US3892760A - Bis-(2-pyridyl-1-oxide) disulfide - Google Patents

Bis-(2-pyridyl-1-oxide) disulfide Download PDF

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Publication number
US3892760A
US3892760A US466328A US46632874A US3892760A US 3892760 A US3892760 A US 3892760A US 466328 A US466328 A US 466328A US 46632874 A US46632874 A US 46632874A US 3892760 A US3892760 A US 3892760A
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Prior art keywords
oxide
alkali metal
disulfide
hydrogen peroxide
bis
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Expired - Lifetime
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US466328A
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Jr Haywood Hooks
James J Pitts
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Olin Corp
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Olin Corp
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Priority to US466328A priority Critical patent/US3892760A/en
Priority to IL46996A priority patent/IL46996A/en
Priority to ZA00752024A priority patent/ZA752024B/en
Priority to IE716/75A priority patent/IE41103B1/en
Priority to CA223,892A priority patent/CA1052792A/en
Priority to GB1439675A priority patent/GB1469907A/en
Priority to AU79968/75A priority patent/AU484367B2/en
Priority to DK168275A priority patent/DK143650C/en
Priority to NL7504696A priority patent/NL7504696A/en
Priority to IT49240/75A priority patent/IT1035419B/en
Priority to FI751253A priority patent/FI58917C/en
Priority to BR3288/75D priority patent/BR7502591A/en
Priority to FR7513649A priority patent/FR2269525B1/fr
Priority to CH554575A priority patent/CH597190A5/xx
Priority to JP5307175A priority patent/JPS5421344B2/ja
Priority to SE7505136A priority patent/SE401508B/en
Priority to BE156038A priority patent/BE828695A/en
Priority to DE19752519715 priority patent/DE2519715C3/en
Application granted granted Critical
Publication of US3892760A publication Critical patent/US3892760A/en
Priority to AR20854677D priority patent/AR208546A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom

Definitions

  • 3,759,932 also generally discloses the preparation of a disulfide compound using an in.-situ preparation technique wherein? mercaptopyridine is not "isolated. -rWh-ile these references broadly disclose the preparati'on' of the disulfide, problems have arisen when using the alkali metal salt of Z-mercaptopyridine-l-oxide in an in-situ technique wherein the alkali metal salt was obtained by oxidizing 2-chloropyridine with permaleic acid ,to form the N- oxide followed by mercaptization to form the salt.
  • oxidationby the; known techniques as shown for,example in U.S. Pat. No. 2,742,476 resulted in the formation of undesired by-products such as the alkali metal maleate and alkali-metal fumarate. This contaminated the desired disulfideproduct and lowered the yield.
  • drosulfide in accordance with known procedures as disclosed if] Us; Pat. No. 2,686,786.1"he'key step in this invention is the oxidation ofjthe preparedlalkali metal salt of2-mercaptopyridinel' oxide using hydrogen peroxide and a reaction pH of about i to about 5.
  • a reaction pH of about i to about 5.
  • the hydrogen peroxide concentration may be varied with about 5 to about 30 percent in aqueous solution being generally used. Generally a stoichiometi' ric. ratio of the alkali metal salt of 2-mercaptopyridine and hydrogen peroxide of about 2 moles of the mercaptopyri dine salt to about 1 mole of peroxide or a slight excess of up to about 15 percent peroxide is used.
  • the pH of the reaction mixture is generally adjusted before the peroxide oxidation step by using any suitable acidifying agent such as the non-oxidizing mineral acids such as HCl andthe non-oxidizing organic acids.
  • the 'disulf ed compounds prepared in accordance with the method of this invention have a variety of known uses, particularly as antibacterialand antifungal agentsin a variety of applications such as to combat agricultural plant diseases, and in plastics and fabrics to resist mildew or other fungus attack as disclosedin U.S. Pat. No. 2,742,476.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Cosmetics (AREA)

Abstract

An improved integrated route to bis-(2-pyridyl-1-oxide) disulfide is provided by oxidizing 2-chloropyridine with permaleic acid to form 2-chloropyridine-1-oxide followed by mercaptization with a selected alkali metal sulfide to form the alkali metal salt of 2-mercaptopyridine-1-oxide and then oxidation with hydrogen peroxide under selected pH conditions.

Description

United States Patent Hooks, Jr. et al.
BIS-(Z-PYRIDYL-l-OXIDE) DISULFIDE Inventors: Haywood Hooks, Jr., West Haven;
James J. Pitts, Hamden, both of Conn.
Olin Corporation, New Haven,
Conn.
Filed: May 2, 1974 Appl. No.: 466,328
Assignee:
U.S. Cl. ..260/294.8 J; 260/290 HL; 260/294.8 G Int. Cl. C07D 211/70 Field of Search. 260/294.8 J, 290 l-lL, 294.8 G
References Cited UNITED STATES PATENTS 8/1954 Shaw et a1. 260/294.8 G
[ July 1,1975
2,742,476 4/1956 Bernstein et a]. 260/2943 .1 2,951,844 9/1960 Sherme'r 260/290 HL 3,759,932 9/]973 Gavin et a]. 260/2948 G Primary Examiner-Alan L. Rotman Attorney, Agent, or Firm-Robert L. Andersen 5 7] ABSTRACT to bis-(2-pyridyl-lby oxidizing 2- 8 Claims, No Drawings BIS-(Z-PYRIDY-L-l-OXIDE) DISULFIDE wherein mercaptopyridine-l-oxide is reacted with an oxidizing'agent. U.S. Pat. No. 3,759,932 also generally discloses the preparation of a disulfide compound using an in.-situ preparation technique wherein? mercaptopyridine is not "isolated. -rWh-ile these references broadly disclose the preparati'on' of the disulfide, problems have arisen when using the alkali metal salt of Z-mercaptopyridine-l-oxide in an in-situ technique wherein the alkali metal salt was obtained by oxidizing 2-chloropyridine with permaleic acid ,to form the N- oxide followed by mercaptization to form the salt. When using this system, oxidationby the; known techniques as shown for,example in U.S. Pat. No. 2,742,476 resulted in the formation of undesired by-products such as the alkali metal maleate and alkali-metal fumarate. This contaminated the desired disulfideproduct and lowered the yield. K
lthas now been found that-when using permaleic acid in the preparation of 2-chloropyridine-l-oxide during the integrated preparation of the disulfide, the above noted by-product formation can be avoided and surprisingly high yields obtained by operating the final oxidation in the presence of hydrogen peroxide at selected 1 pH conditions. More particularly the oxidation .of the alkali metal salt of 'zrrierc aptopyridine-l-oxide is carried out at a pH of about 4 to about 5 and preferably from about 4.5 to about 5. The overall reaction scheme of this invention is illustrated by the following equation:
drosulfide in accordance with known procedures as disclosed if] Us; Pat. No. 2,686,786.1"he'key step in this invention is the oxidation ofjthe preparedlalkali metal salt of2-mercaptopyridinel' oxide using hydrogen peroxide and a reaction pH of about i to about 5. By main? taining. the reaction under these conditions, the'precipitation of unde's i're'd impurities, primarily derived from the salts of fumaricacid is avoided and surprisingly high yields resulted. a g 3' In carrying out thereactionof this inventior -the temperature may generally be maintained fromabout 15 to about 35C. with about 20 to about 30C being preferred. The hydrogen peroxide concentration may be varied with about 5 to about 30 percent in aqueous solution being generally used. Generally a stoichiometi' ric. ratio of the alkali metal salt of 2-mercaptopyridine and hydrogen peroxide of about 2 moles of the mercaptopyri dine salt to about 1 mole of peroxide or a slight excess of up to about 15 percent peroxide is used.
It is alsojgenerally advisable to agitate the reaction mixture in the peroxide oxidation step to maintain an effectively dilute hydrogen peroxide solution. 1
The pH of the reaction mixture is generally adjusted before the peroxide oxidation step by using any suitable acidifying agent such as the non-oxidizing mineral acids such as HCl andthe non-oxidizing organic acids.
While '2-chloropyridine has been shown to be a desired starting material in the method {of this invention. other -2-halopyridine's* and substituted halopy ridines containing groups such as lower alkyl and lower alkoxy which do not adversely affect the reaction may also be used.
Isolation of the final product after oxidation is obtained by a standard filtration procedure.
The 'disulf ed compounds prepared in accordance with the method of this invention have a variety of known uses, particularly as antibacterialand antifungal agentsin a variety of applications such as to combat agricultural plant diseases, and in plastics and fabrics to resist mildew or other fungus attack as disclosedin U.S. Pat. No. 2,742,476.
The following examples are further illustrative of this invention.
EXAMPLE I A 2-liter, 3-neck flask fitted with a stirrer, thermometer and addition funnel was charged with 1,866 g of a reaction mixture containing the sodium salt of 2-mercaptopyridine-l-oxide. This reaction mixture had an assay of 7.2 percent 135 g) of the sodium salt of 2-mercaptopyridine-l-oxide, 7 percent sodium chloride and 13-14 percent total of sodium maleate and sodium fumarate. This mixture was obtained by oxidizing 2-chloropyridine with permaleic acid and then mercaptizing with NaSH. The pH was then adjusted to 4.5 with concentrated hydrochloric acid and the resulting warm solution was cooled to 25C. and 52 ml. of30 percent hydrogen peroxide 12 percent excess over stoichiometry) in l60 ml. water added dropwise over a 30 minute period with stirring. The reaction was slightly exothermic with the temperature rising to approximately 30C. at the end of the peroxide addition. Stirring of the now precipitated bis-(2-pyridyl-l-oxide) disulfide product was continued for 2 more hours to assure completeness of the reaction. The disulfide product formed was collected by filtration and the filter cake washed with 50 ml. water follower by 50 ml of methanol. After air drying, a total of 1 12 g (98 percent yield based on starting sodium salt of 2-mercaptopyridine-l-oxide) of bis-(Z-pyridyl-l-oxide) disulfide was obtained with a melting point of 20020lC. and an assay of 98 percent.
EXAMPLE ll Using the same procedure as Example I with a reaction mixture containing 25.6 g of the sodium salt of Z-mercaptopyridine-l-oxide, 14 g of percent hydrogen peroxide, a pH of 4.0 and a reaction time of 18 hours, 17.0 g of the disulfide product was obtained (79.8 percent yield based on sodium salt) having as assay of 97.8 percent.
EXAMPLE lll Using the same procedure Example I with a reaction mixture containing 25.6 g of the sodium salt of 2-mercaptopyridine-l-oxide, 14 g of 10 percent hydrogen peroxide, a pH of 5.0, a reaction temperature of 20 to 23C. and a reaction time of 18 hours, 19.0 g of the disulfide product was obtained (89.3 percent yield based on sodium salt) and an assay of 97.7 percent.
EXAMPLE [V For comparative purposes, the same procedure as Example II was followed with a pH of 3.0. A product of 23.5 g was obtained, however, it was contaminated with significant quantities of furmaric acid impurities.
EXAMPLE V For, comparative purposes, the same procuedure as Example III was followed with a pH of 5.5 and a reaction time of 72 hours. A product of 10.5 g (49.3 percent yield) was obtained.
What is claimed is:
1. In the method of preparing bis-(Z-pyridyll -oxide) disulfide wherein 2-chloropyridine is oxidized with permaleic acid to form a reaction mixture containing 2- chloropyridine-l-oxide which is mercaptized usingan alkali metal sulfide or alkali metal hydrosulfide to form the alkali metal salt of.Z-mercaptopyridine-l-oxide in solution, the improvement comprising adjusting the pH of the resulting solution to a pH of about 4 to about 5 and then oxidizing with hydrogen peroxide to form the bis-(Z-pyridyl-l-oxide) disulfide compound.
2. The method of claim 1 wherein said alkali metal is sodium.
3. The method of claim 2 wherein a pH of about 4.5 to about 5 is used.
4. The method of claim 2 wherein said hydrogen peroxide oxidation is carried out at a temperature of from about 15 to about 35C.
5. The method of claim 4 wherein a hydrogen peroxide concentration of from about 5 to about 30 percent in aqueous solution is used.
6. The method of claim 5 wherein said resulting solution contains sodium fumarate and sodium maleate in addition to the sodium 'salt of 2-mercaptopyridine-loxide.
7. The method of claim 5 wherein a pH of about 4.5 to about 5 is used.
8. The method of claim 7 wherein a temperature of from about 20 to about 30C. is used.

Claims (8)

1. IN THE METHOD OF PREPARING BIS-(2PYRIDYL-1-OXIDE) DISULFIDE WHEREIN 2-CHLOROPYRIDINE IS OXIDIZED WITH PERMALEIC ACID TO FORM A REACTION MIXTURE CONTAINING 2-CHLOROPYRIDINE-1OXIDE WHICH IS MERCAPTIZED USING AN ALKALI METAL SULFIDE OR ALKALI METAL HYDROSULFIDE TO FORM THE ALKALI METAL SALT OF 2MERCAPTOPYRIDINE-1-OXIDE IN SOLUTION, THE IMPROVEMENT COMPRISING ADJUSTING THE PH OF THE RESULTING SOLUTION TO A PH OF ABOUT 4 TO ABOUT 5 AND THEN OXIDIZING WITH HYDROGEN PEROXIDE TO FORM THE BIS-(2PYRIDYL-1-OXIDE) DISULFIDE COMPOUND.
2. The method of claim 1 wherein said alkali metal is sodium.
3. The method of claim 2 wherein a pH of about 4.5 to about 5 is used.
4. The method of claim 2 wherein said hydrogen peroxide oxidation is carried out at a temperature of from about 15* to about 35*C.
5. The method of claim 4 wherein a hydrogen peroxide concentration of from about 5 to about 30 percent in aqueous solution is used.
6. The method of claim 5 wherein said resulting solution contains sodium fumarate and sodium maleate in addition to the sodium salt of 2-mercaptopyridine-1-oxide.
7. The method of claim 5 wherein a pH of about 4.5 to about 5 is used.
8. The method of claim 7 wherein a temperature of from about 20* to about 30*C. is used.
US466328A 1974-05-02 1974-05-02 Bis-(2-pyridyl-1-oxide) disulfide Expired - Lifetime US3892760A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
US466328A US3892760A (en) 1974-05-02 1974-05-02 Bis-(2-pyridyl-1-oxide) disulfide
IL46996A IL46996A (en) 1974-05-02 1975-04-01 Method for preparing bis-(2-pyridyl-1-oxide)disulfide
ZA00752024A ZA752024B (en) 1974-05-02 1975-04-01 Method for preparing bigs-(2-pyridyl-1-oxide) disufide
IE716/75A IE41103B1 (en) 1974-05-02 1975-04-02 Method for preparing bis-(2-pyridyl-1-oxide) disulfide
CA223,892A CA1052792A (en) 1974-05-02 1975-04-04 Method for preparing bis-(2-pyridyl-1-oxide) disulfide
GB1439675A GB1469907A (en) 1974-05-02 1975-04-08 Method for preparing bis-2-pyridyl-1-oxide- disulphide
AU79968/75A AU484367B2 (en) 1974-05-02 1975-04-09 METHOD FOR PREPARING BIS-(2-PYRIDYL-l-OXIDE DISULFIDE
DK168275A DK143650C (en) 1974-05-02 1975-04-18 Process for the preparation of bis- (2-pyridyl-1-oxide) disulfide
NL7504696A NL7504696A (en) 1974-05-02 1975-04-21 PROCESS FOR THE PREPARATION OF BIS (2-PYRIDYL--1-OXIDE) DISULPHIDE.
IT49240/75A IT1035419B (en) 1974-05-02 1975-04-22 PROCEDURE FOR THE PRODUCTION OF BIS 2 PYRIDYL I OXIDE OF SOL FURO
FI751253A FI58917C (en) 1974-05-02 1975-04-25 PROCEDURE FOR FRAMSTAELLNING AV BIS- (2-PYRIDYL-1-OXID) DISULFID
BR3288/75D BR7502591A (en) 1974-05-02 1975-04-29 IMPROVEMENT IN THE PROCESS OF PREPARING BIS- (1-2-PYRIDYL OXIDE) DISSULPHIDE
FR7513649A FR2269525B1 (en) 1974-05-02 1975-04-30
CH554575A CH597190A5 (en) 1974-05-02 1975-04-30
JP5307175A JPS5421344B2 (en) 1974-05-02 1975-05-01
SE7505136A SE401508B (en) 1974-05-02 1975-05-02 PROCEDURE FOR BIS PREPARATION (2-PYRIDYL-1-OXIDE) -DISULFID
BE156038A BE828695A (en) 1974-05-02 1975-05-02 PREPARATION OF BIS- (2-PYRIDYL-1-OXYDE) DISULFIDE
DE19752519715 DE2519715C3 (en) 1974-05-02 1975-05-02 Process for the preparation of bis (2-pyridyl-1-oxide) disulfide
AR20854677D AR208546A1 (en) 1974-05-02 1977-02-15 BIS- (2-PYRIDYL-1-OXIDE) DISULFIDE PREPARATION METHOD

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US466328A US3892760A (en) 1974-05-02 1974-05-02 Bis-(2-pyridyl-1-oxide) disulfide

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CA (1) CA1052792A (en)
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IE (1) IE41103B1 (en)
IL (1) IL46996A (en)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4504667A (en) * 1983-06-24 1985-03-12 Olin Corporation Process for oxidizing halopyridines to halopyridine-N-oxides
US4585871A (en) * 1982-03-26 1986-04-29 Olin Corporation Process for oxidizing halopyridines to halopyridine-N-oxides
US6664280B2 (en) 2001-07-25 2003-12-16 The United States Of America As Represented By The Secretary Of The Army Antivesicant compounds and methods of making and using thereof
US20040171600A1 (en) * 2001-03-06 2004-09-02 Toshimasa Ohnishi Antimicrobial compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2686786A (en) * 1953-01-09 1954-08-17 Olin Mathieson Nu-hydroxy-2-pyridinethiones and method of preparing same
US2742476A (en) * 1953-10-26 1956-04-17 Olin Mathieson Derivatives of 2-mercaptopyridine 1-oxide
US2951844A (en) * 1958-11-05 1960-09-06 Olin Mathieson Cyclic process for manufacture of 2-chloropyridine-1-oxide
US3759932A (en) * 1972-08-25 1973-09-18 Olin Corp Method for preparing mercaptopyridines using alkali metal polysulfides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1224744B (en) * 1956-04-13 1966-09-15 Olin Mathieson Process for the preparation of bactericidal and fungicidal sulfur-containing pyridine compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2686786A (en) * 1953-01-09 1954-08-17 Olin Mathieson Nu-hydroxy-2-pyridinethiones and method of preparing same
US2742476A (en) * 1953-10-26 1956-04-17 Olin Mathieson Derivatives of 2-mercaptopyridine 1-oxide
US2951844A (en) * 1958-11-05 1960-09-06 Olin Mathieson Cyclic process for manufacture of 2-chloropyridine-1-oxide
US3759932A (en) * 1972-08-25 1973-09-18 Olin Corp Method for preparing mercaptopyridines using alkali metal polysulfides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4585871A (en) * 1982-03-26 1986-04-29 Olin Corporation Process for oxidizing halopyridines to halopyridine-N-oxides
US4504667A (en) * 1983-06-24 1985-03-12 Olin Corporation Process for oxidizing halopyridines to halopyridine-N-oxides
US20040171600A1 (en) * 2001-03-06 2004-09-02 Toshimasa Ohnishi Antimicrobial compositions
US7416736B2 (en) * 2001-03-06 2008-08-26 Janssen Pharmaceutica N.V. Antimicrobial compositions
US6664280B2 (en) 2001-07-25 2003-12-16 The United States Of America As Represented By The Secretary Of The Army Antivesicant compounds and methods of making and using thereof

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DE2519715B2 (en) 1977-03-31
AR208546A1 (en) 1977-02-15
JPS50149680A (en) 1975-11-29
IE41103B1 (en) 1979-10-24
CH597190A5 (en) 1978-03-31
NL7504696A (en) 1975-11-04
AU7996875A (en) 1976-10-14
DK168275A (en) 1975-11-03
BR7502591A (en) 1976-03-16
SE401508B (en) 1978-05-16
IT1035419B (en) 1979-10-20
IL46996A0 (en) 1975-06-25
FR2269525B1 (en) 1979-10-05
GB1469907A (en) 1977-04-06
DK143650C (en) 1982-02-15
FI58917B (en) 1981-01-30
CA1052792A (en) 1979-04-17
FI58917C (en) 1981-05-11
BE828695A (en) 1975-11-03
JPS5421344B2 (en) 1979-07-30
SE7505136L (en) 1975-11-03
IL46996A (en) 1977-12-30
IE41103L (en) 1975-11-02
ZA752024B (en) 1976-02-25
DK143650B (en) 1981-09-21
FI751253A (en) 1975-11-03
FR2269525A1 (en) 1975-11-28
DE2519715A1 (en) 1975-11-06

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