GB2161802A - Process for producing N-chlorosulfenyl compounds - Google Patents
Process for producing N-chlorosulfenyl compounds Download PDFInfo
- Publication number
- GB2161802A GB2161802A GB08418512A GB8418512A GB2161802A GB 2161802 A GB2161802 A GB 2161802A GB 08418512 A GB08418512 A GB 08418512A GB 8418512 A GB8418512 A GB 8418512A GB 2161802 A GB2161802 A GB 2161802A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- sulfur dichloride
- process according
- reaction
- amino compound
- 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
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 29
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl Chemical group 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 4
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 4
- 230000000749 insecticidal effect Effects 0.000 abstract description 4
- 230000000895 acaricidal effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VNYJDSJLCWDYJK-UHFFFAOYSA-N Methyl 2-[(2-methoxy-2-oxoethyl)amino]acetate Chemical compound COC(=O)CNCC(=O)OC VNYJDSJLCWDYJK-UHFFFAOYSA-N 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YAUWHXKOYHADTR-UHFFFAOYSA-N butyl n-methylcarbamate Chemical compound CCCCOC(=O)NC YAUWHXKOYHADTR-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- BGEHOKVPALSAIX-UHFFFAOYSA-N ethyl 3-(propan-2-ylamino)propanoate Chemical compound CCOC(=O)CCNC(C)C BGEHOKVPALSAIX-UHFFFAOYSA-N 0.000 description 1
- JGRPZAGOYKNIAC-UHFFFAOYSA-N ethyl n-propan-2-ylcarbamate Chemical compound CCOC(=O)NC(C)C JGRPZAGOYKNIAC-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/86—Benzo [b] furans; Hydrogenated benzo [b] furans with an oxygen atom directly attached in position 7
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
N-chlorosulfenyl compounds of the formula <IMAGE> in which R1 is alkyl, alkoxycarbonyl, alkoxycarbonylalkyl or 2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl, and R2 is alkyl or alkoxycarbonylalkyl, are produced by reaction of an amino compound of the formula <IMAGE> with sulfur dichloride. The reaction is performed in excess sulfur dichloride as solvent and in the absence of a base. The formed N-chlorosulfenyl compounds of the above formula are intermediates for insecticidal and acaricidal active substances.
Description
SPECIFICATION
Process for producing N-chlorosulfenyl compounds
The present invention relates to a process for producing N-chlorosulfenyl compounds of the formula
in which R, is C1-C8-alkyl, C1-CB-alkoxycarbonyl, Cl-C6-alkoxycarbonyl, -C -C6-alkyl or 2,3-dihydro-2,2 di methyl benzofuran-7-yloxycarbonyl, and R2 is C -C8-alkyl or C -C1 C - C8-alkoxycarbonyl-C1C6-alkyl.
The N-chlorosulfenyl compounds of the formula I are intermediates for producing N,N-sulfides which are distinguished by a marked insecticidal and acaricidal action. To be mentioned as active substances of this kind are for example: 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methyl-N-(N-methyl-N-butoxyCar- bonylami nosu If enyl)-ca rba mate, 2,3-dihydro- 2,2-dihydro-2,2-dimethylbenzofuran-7-yl-N-methyl-N-(N,N-di- butylaminosulfe nyl-carbamate and 2,3-dihydro-2,2-dimethylbenzofuran-7-yI-N-methyl- N-( Nethoxycarbonylethyl-N-isopropylaminosulfenyl)-carbamate. Such insecticidal active substances, the production thereof and their use are described for example in the British Patent Specifications Nos.
1,583,713 and 2,084,134, and in the U.S. Patent Specification No. 4,006,231.
It is known that N-chlorosulfenyl compounds can be produced from carbamates by dissolving the carbamate and the essentially equivalent amount of sulfur dichloride in an inert solvent, for example methylene chloride, and feeding into this solution a base, for example pyridine, in controlled amounts. After completion of the reaction, the hydrochloride of the base is filtered off; the solvent is then distilled off and the crude product purified by distillation (cp. U.S. Patent No. 3,843,688).
Also known is the method of producing N-chlorosulfenyl compounds from carbamoyl halides by taking the carbamoyl halide and sulfur dichloride in a molar ratio of 1:2, and introducing into this mixture, with cooling, a base, such as a tert-alkylamine, pyridine or lutidine. After the reaction has finished, the bulk of the unreacted sulfur dichloride is distilled off, and from the residue is then obtained a crude product by further distillation, this product containing, beside the desired N-chloro- sulfenylcarbamoyl halide, considerable amounts of sulfur monochloride (52Cl2) and a small amount of sulfur dichloride. From this crude product is obtained pure N-chloro-sulfenylcarbamoyl halide by chlorinating the sulfur monochloride to sulfur dichloride, and separating this by distillation (cp. U.S. Patent No. 4,333,883).
Finally, it is also known that N-chlorosulfenyl compounds can be produced from dialkylamines by firstly converting a dialkylamine by reaction with sulfur monochloride into the corresponding N,N-disulfide, and subsequently converting this by reaction with a chlorinating agent, such as chlorine or sulfuryl chloride, into the corresponding dialkylamino -sulfenyl chloride (cp. European Patent Application No.
0,051,273).
According to the present invention, a process for producing N- chlorosulfenyl compounds of the formula I is suggested, which is based on the reaction of an amino compound of the formula II.
in which R1 and R2 have the meanings defined under the formula I, with sulfur dichloride, which process comprises performing the reaction of the amino compound of the formula II with sulfur dichloride at 10 60"C, in excess sulfur dichloride as solvent and in the absence of a base, and obtaining the N-chlorosulfenyl compound of the formula I by evaporating off the unreacted sulfur dichloride.
The process according to the invention is advantageously performed by taking the sulfur dichloride and slowly adding the amino compound of the formula II in controlled amounts. The excess of sulfur dichloride can vary within wide limits, with no critical upper limit existing with regard to the technical practicability of the process. The limit is therefore determined primarily by economic factors. In the carrying out of the process according to the invention, there can thus us used as a rule 1.25 - 10.0 mols of sulfur dichloride per mol of the amino compound of the formula II. There are used advantageously 1.5 5.0 mols of sulfur chloride per mol of the amino compound of the formula II, and particularly advantageously 1.6 - 2.0 mols of sulfur dichloride per mol of amino compound of the formula II.
Within the given temperature range of 10-60"C, in which the process according to the invention can be performed, temperatures of 25-50"C and especially temperatures of 30-40"C are preferred.
After the completed reaction of the amino compound of the formula II with the sulfur dichloride, the distilling off of the excess sulfur dichloride can be performed at normal pressure or under reduced pres sure. In order to avoid high temperatures, and in view of the fact that sulfur dichloride (boiling point: 59"C) readily decomposes with the formation of sulfur monochloride (S2CI2; boiling point: 139 C) and chlorine, it is advantageous to distill off the excess sulfur dichloride at the lowest possible temperature under reduced pressure, for example under a pressure of 100-300 mbar.
The sulfur dichloride distilled off from the reaction mixture can be recycled and used for a further reac- tion with an amino compound of the formula II. Since also with distillation under reduced pressure, the sulfur dichloride partially decomposes into sulfur monochloride and chlorine, it is necessary before recycling to treat the resulting distillate with a chlorinating agent, such as chlorine gas or sulfuryl chloride, in order to convert the sulfur monochloride present into sulfur dichloride. For this chlorination it is also possible to re-use the chlorine formed during decomposition of sulfur dichloride.
The N-chlorosulfenyl compounds of the formula I obtained after the excess sulfur dichloride has been distilled off are already of high purity, and can therefore as a rule be used directly for further reaction to give an insecticidal active substance. If necessary, however, the N- chlorosulfenyl compounds of the formula I can also be purified by distillation before they are further processed.
The process according to the invention can be carried out either discontinuously (batchwise) or continuously. It is suitable in particular for continous operation since the sulfur dichloride distilled off from the reaction mixture can be recycled, after a chlorination treatment, for further use in the process.
The process according to the invention is suitable for producing the N- chlorosulfenyl compounds of the formula I on a commercial scale in a simple manner and in good yield and quality. Compared with known processes, the process according to the invention is distinguished particularly by the simplicity of the further processing of the reaction mixture obtained after completion of the reaction of an amino com pound of the reaction of an amino compound of the formula II with excess sulfur dichloride. This further processing is limited to a simple distillation since neither a salt of a base nor an organic solvent has to be separated off.
The recovery, necessary in the prior known processes, of the base used as an acid-binding agent, and also the purification of the base and of the organic solvent, are thus avoided. The mixture of sulfur dich chloride and sulfur monochloride, obtained on final distillation, can be converted in a simple manner, by treatment with a chlorinating agent, into directly re-usable sulfur dichloride. By application of the procedure according to the invention, side reactions are largely avoided, and the N-chlorosulfenyl compounds of the formula I are obtained in excellent yield and with a high degree of purity.
The process according to the invention is further illustrated by the following Examples.
Example 1: Production of n-butyl-N-methyl-N-chloro-sulfenyl) carbamate
280 kg (2.7 kilomols) of sulfur dichloride are placed into a 630 litre enameled vessel, and at 300C are added in controlled amounts from a feed vessel, within 5 hours, 196.5 kg (1.5 kilomols) of n-butyl-Nmethyl carbamate. After completion of the addition, the internal temperature is raised subsequently distilled off at 40"C and 200 mbar 120 kg of sulfur dichloride and formed sulfur monochloride. The crude nbutyl-(N-methyl-N-chlorsulfenyl)-carbamate obtained as residue is purified by distillation under high vacuum (0.5 mbar; 74-76"C). There are obtained 255.0kg of 97-98% pure n-butyl-(N-methyl-N-chlorosulfenyl)carbamate, the yield being 85% of theory, relative to the employed n- butyl-N-methyl carbamate.
The mixture of sulfur dichloride and sulfur monochloride distilled off from the reaction mixture is converted, by the introduction of 40.0 kg of chlorine at 0-5"C, again into sulfur dichloride, which can be used for further reactions.
In a manner analogous to that described in Example 1, the following amino compounds of the formula
II are converted into the corresponding N- chlorosulfenyl compounds of the formula I: di-n-butylamine,
N-(2-ethoxycarbo nylethyl )-isop ropylamine, 2,3-dihydro-2,2-dimethyl benzofu ran-2-yl-N-methyl carbamate, di-n-octylamine, n-propyl-N-ethyl carbamate, methy-N-n-butyl carbamate
N-ethoxycarbonylmethyl-methylamine, bis-(methoxycarbonylmethyl)-amine, bis-(methoxyca rbonylethyl)-a mine, ethy-N-methyl carbamate, n-octylN-methyl carbamate, and ethyl-N-isopropyl carbamate.
Claims (10)
1. A process for for producing an N-chlorosulfenyl compound of the formula
in which B1 is C1 -C8-alkyl, C, - C8-alkoxycarbonyl, C1 - Calkoxycarbonyl-C, - Cral kyl or 2,3-dihydro- 2,2-di methylbenzofuran-7-yloxycarbonyl, and R2 is C,-C8- alkyl or C1 C8-alkoxycarbonyl-CI-Cfi-alkyl, by reaction of anamino compound of the formula II.
in which R, and R2 have the meanings defined under the formula I, with sulfur dichloride, which process comprises performing the reaction of the amino compound of the formula II with sulfur chloride at 10 60"C, in excess sulfur dichloride as solvent and in the absence of a base, and obtaining the formed Nchlorosulfenyl compound of the formula I by evaporating off the unreacted sulfur dichloride.
2. A process according to Claim 1, wherein 1.25 -10.0 mols of sulfur dichloride are used per mol of the amino compound of the formula II.
3. A process according to Claim 1, wherein 1.5 -5.0 mols of sulfur chloride are used per mol of the amino compound of the formula II.
4. A process according to Claim 3, wherein 1.6 -2.0 mols of sulfur dichloride are used per mol of the amino compound of the formula II.
5. A process according to Claim 1, wherein the sulfur dichloride is placed into the reaction vessel and the amino compound of the formula II is slowly added in controlled amounts.
6. A process according to Claim 1, wherein the reaction of the sulfur dichloride with the amino compound of the formula II is performed at a temperature of 25-50"C.
7. A process according to Claim 6, wherein the reaction of the sulfur dichloride with the amino compound of the formula II is performed at a temperature of 30-40"C.
8. A process according to Claim 1, wherein, after the reaction of the sulfur dichloride with the amino compound of the formula II, the unreacted sulfur dichloride is distilled off under reduced pressure from the reaction mixture.
9. A process according to claim 1 substantially as hereinbefore described with reference to the foregoing Example.
10. An N-chlorosulfenyl compound of the formula (I) defined in claim 1 whenever prepared by a process according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08418512A GB2161802B (en) | 1984-07-20 | 1984-07-20 | Process for producing n-chlorosulfenyl compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08418512A GB2161802B (en) | 1984-07-20 | 1984-07-20 | Process for producing n-chlorosulfenyl compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8418512D0 GB8418512D0 (en) | 1984-08-22 |
| GB2161802A true GB2161802A (en) | 1986-01-22 |
| GB2161802B GB2161802B (en) | 1987-07-15 |
Family
ID=10564175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08418512A Expired GB2161802B (en) | 1984-07-20 | 1984-07-20 | Process for producing n-chlorosulfenyl compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2161802B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008108448A1 (en) | 2007-03-07 | 2008-09-12 | Nissan Chemical Industries, Ltd. | Isoxazoline-substituted benzamide compound and pest control agent |
| WO2009005015A1 (en) | 2007-06-29 | 2009-01-08 | Nissan Chemical Industries, Ltd. | Substituted isoxazoline or enone oxime compound, and pest control agent |
| WO2009072621A1 (en) | 2007-12-07 | 2009-06-11 | Nissan Chemical Industries, Ltd. | Substituted dihydroazole compound and pest control agent |
| WO2014010737A1 (en) | 2012-07-12 | 2014-01-16 | 日産化学工業株式会社 | Oxime-substituted amide compound and pest control agent |
-
1984
- 1984-07-20 GB GB08418512A patent/GB2161802B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008108448A1 (en) | 2007-03-07 | 2008-09-12 | Nissan Chemical Industries, Ltd. | Isoxazoline-substituted benzamide compound and pest control agent |
| WO2009005015A1 (en) | 2007-06-29 | 2009-01-08 | Nissan Chemical Industries, Ltd. | Substituted isoxazoline or enone oxime compound, and pest control agent |
| US8053452B2 (en) | 2007-06-29 | 2011-11-08 | Nissan Chemical Industries, Ltd. | Substituted isoxazoline or enone oxime compound, and pest control agent |
| WO2009072621A1 (en) | 2007-12-07 | 2009-06-11 | Nissan Chemical Industries, Ltd. | Substituted dihydroazole compound and pest control agent |
| WO2014010737A1 (en) | 2012-07-12 | 2014-01-16 | 日産化学工業株式会社 | Oxime-substituted amide compound and pest control agent |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2161802B (en) | 1987-07-15 |
| GB8418512D0 (en) | 1984-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940720 |