CN106045887A - Synthesis method of N-ethylsulfenamide compounds - Google Patents
Synthesis method of N-ethylsulfenamide compounds Download PDFInfo
- Publication number
- CN106045887A CN106045887A CN201610496568.6A CN201610496568A CN106045887A CN 106045887 A CN106045887 A CN 106045887A CN 201610496568 A CN201610496568 A CN 201610496568A CN 106045887 A CN106045887 A CN 106045887A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- compound
- formula
- alkali
- catalyst
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/08—Sulfenic acids; Derivatives thereof
- C07C313/18—Sulfenamides
- C07C313/26—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C313/28—Y being a hydrogen or a carbon atom
Abstract
The invention relates to a synthesis method of N-ethylsulfenamide compounds disclosed as Formula (III). The method comprises the following steps: in an organic solvent, carrying out reaction on compounds disclosd as Formula (I) and compounds disclosed as Formula (II) in the presence of a catalyst, an alkali, aids and an activator; and after the reaction finishes, carrying out after-treatment to obtain the compounds disclosed as Formula (III), wherein R1 is selected from H, C1-C6 alkyl, C1-C6 alkoxy or halogen. By adopting the specific reaction compounds, the catalyst, alkali, aids, organic solvent and activator are comprehensively selected to obtain the target products at high yield, thereby providing a brand-new way for synthesizing the compounds, and having wide practical application value.
Description
Technical field
The present invention relates to the synthetic method of a kind of sulfur-containing compound, relate more particularly to a kind of N-second sulfenamide chemical combination
The synthetic method of thing, belongs to organic chemical synthesis field.
Background technology
The sulfenamide compounds of electron deficiency usually has good biological activity, prodrug activity, and can be as medicine
Conventional intermediate in synthesis.Such as, following compound i.e. shows the antibacterial activity of excellence,
Therefore, the synthetic method of exploitation sulfenamide compounds will be to organic synthesis, the production of such as medicine intermediate
Etc. aspect produce active influence, be also a long-term and challenging job for numerous scientific research personnel simultaneously.
Up to now, prior art has been developed for the multiple catalysis for synthesizing electron deficiency sulfenamide compound anti-
Induction method.Such as:
(" Exploration of the " Traceless " the Reductive Ligation of S-such as Zhang Jiming
Nitrosothiols ", Organic Letters, 2009,11,477-480) report one with S-nitrosothiol class chemical combination
Thing is that raw material reacts the method building sulfenamide compounds, and its reaction equation is as follows:
Additionally, (" the Selective and Scalable Synthesis of Trifl such as Roman Pluta
uoromethanesulfenamides and Fluorinated Unsymmetrical Disulfides using a
Shelf-Stable Electrophilic SCF3Reagent ", Chem.Eur.J., 2004,20,17315-17318) report
A kind of synthetic method of sulfenamide compounds, its reaction equation is as follows:
But, the reaction process condition of these methods existing is the harshest, and yield is to be improved, substrate source need into
The problems such as one step extension.
Thinkings based on these problems, the invention provides the synthetic method of a kind of N-ethyl sulfenamide compounds,
This kind of method uses N-ethyl-formamide compounds and thio-ether type compounds to be initiation material, in the effect of specific catalyst system and catalyzing
Under, it is achieved that the high yield synthesis of N-ethyl formoxyl sulfenamide compounds, there is quite varied actual application value.
It is to be noted that the present invention is the improvement of the another piece patent application applied on the same day, described another piece patent application is led to
Cross and quote and be fully incorporated into.
Summary of the invention
In order to overcome many defects as indicated above, present inventor has performed in-depth study and exploration, paying
After enough creative works, thus complete the present invention.
Specifically, technical scheme and content relate to the sulfenamide of N-ethyl shown in formula (III) under one
The synthetic method of compound, described method includes: in organic solvent, in the presence of catalyst, alkali, auxiliary agent and activator,
Lower formula (I) compound and lower formula (II) compound react, and react after terminating through post processing, thus obtain described formula (III)
Compound,
Wherein, R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to the straight chain with 1-6 carbon atom
Or branched alkyl, can be the most such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl or n-hexyl etc..
In the described synthetic method of the present invention, described C1-C6Alkoxyl then refers to " C defined above1-C6Alkyl " and O
Group after atom is connected, such as methoxyl group, ethyoxyl, positive propoxy, n-butoxy.
In the described synthetic method of the present invention, halogen is fluorine, chlorine, bromine or iodine atom.
In the described synthetic method of the present invention, described catalyst is double (cyclopentadienyl group) zirconium dichloride, dichloro two cyclopentadienyl
Any one in zirconium, double (n-butyl cyclopentadienyl) zirconium dichloride or hexafluoroacetylacetone zirconium, the most double (normal-butyls
Cyclopentadienyl group) zirconium dichloride.
In the described synthetic method of the present invention, described alkali is 1,8-diazabicylo 11 carbon-7-alkene (DBU), Isosorbide-5-Nitrae-
Diazabicylo [2.2.2] octane (DABCO), 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene (TBD), NaOH, the tert-butyl alcohol
Any one in potassium or dimethylamino naphthyridine (DMPA), most preferably Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO).
In the described synthetic method of the present invention, described auxiliary agent is tetraphenylporphyrin and copper trifluoromethanesulfcomposite (Cu (OTf)2)
Mixture, wherein tetraphenylporphyrin and copper trifluoromethanesulfcomposite (Cu (OTf)2) mol ratio be 1:3-4, can be such as 1:3,1:
3.5 or 1:4.
In the described synthetic method of the present invention, described activator is N-sulfonic acid butyl-pyridinium tosilate.
In the described synthetic method of the present invention, described organic solvent is DMF (DMF), dimethyl Asia
In sulfone (DMSO), toluene, benzene, acetonitrile, 1,4-dioxane or polyethylene glycol 200 (PEG-200) any one or the most
The mixture of the mixture planted, the most preferably Isosorbide-5-Nitrae-dioxane of volume ratio 1:2 and polyethylene glycol 200 (PEG-200).
Wherein, the consumption of described organic solvent does not has strict restriction, and those skilled in the art can be according to practical situation
Suitably selecting and determine, such as its consumption size, to facilitate reaction to carry out and post processing, is no longer carried out at this in detail
Thin description.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (II) compound:
1.2-1.8, such as, can be 1:1.2,1:1.5 or 1:1.8.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.04-with the mol ratio of catalyst
0.08, can be such as 1:0.04,1:0.06 or 1:0.08.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.1-0.2 with the mol ratio of alkali, such as
Can be 1:0.1,1:0.15 or 1:0.2.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.08-0.15 with the mol ratio of auxiliary agent,
The mole dosage of the most described formula (I) compound and the tetraphenylporphyrin and the copper trifluoromethanesulfcomposite (Cu (OTf) that constitute described auxiliary agent2)
The ratio of integral molar quantity be 1:0.08-0.15, can be such as 1:0.08,1:0.1,1:0.12,1:0.14 or 1:0.15.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.05-0.1 with the mol ratio of activator,
Can be such as 1:0.05,1:0.07,1:0.09 or 1:0.1.
In the described synthetic method of the present invention, reaction temperature is 70-90 DEG C, such as, can be 70 DEG C, 80 DEG C or 90 DEG C.
In the described synthetic method of the present invention, the response time is 7-10 hour, such as, can be 7 hours, 8 hours, 9 hours
Or 10 hours.
In the described synthetic method of the present invention, the post processing after reaction terminates can be specific as follows: after reaction terminates, will be anti-
Liquid filtered while hot, the pH value of regulation filtrate is answered to neutral, then fully to vibrate with deionized water, add petroleum ether extraction 2-3
Secondary, merge organic facies, concentrating under reduced pressure, gained residue crosses silica gel flash column chromatography, with the acetone of volume ratio 1:3 and mixing of chloroform
Conjunction liquid is rinsed, thus obtains described formula (III) compound.
In sum, the invention provides the synthetic method of a kind of sulfenamide compounds, described method uses specific
Compound of reaction, and by catalyst, alkali, auxiliary agent, activator and the combined selection of organic solvent, such that it is able to high yield obtains
To purpose product, the synthesis for this compounds provides brand-new path, has actual application value widely.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, and not the real protection scope to the present invention constitutes any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Embodiment 1
Under room temperature, to appropriate organic solvent (Isosorbide-5-Nitrae-dioxane and the polyethylene glycol 200 (PEG-200) for volume ratio 1:2
Mixture) in, add the upper formula (I) compound of 100mmol, 150mmol upper formula (II) compound, 6mmol catalyst pair (positive fourth
Cyclopentadienyl group) zirconium dichloride, 15mmol alkali 1,4-diazabicylo [2.2.2] octane (DABCO), 12mmol auxiliary agent (be
2.7mmol tetraphenylporphyrin and 9.3mmol copper trifluoromethanesulfcomposite (Cu (OTf)2) mixture) and 7.5mmol activator N-sulphur
Acid butyl pyridinium p-toluenesulfonate, is then warming up to 80 DEG C under stirring, and stirring reaction 9 hours at such a temperature；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate, to neutral, then fully shakes with deionized water
Swinging, add petroleum ether extraction 2-3 time, merge organic facies, concentrating under reduced pressure, gained residue crosses silica gel flash column chromatography, with body
The mixed liquor amassing the acetone than 1:3 and chloroform is rinsed, thus obtains upper formula (III) compound, and productivity is 92.8%.
1H NMR(CDCl3,400MHz):δ8.44(s,1H),7.32(m,2H),7.24(m,3H),3.58(m,2H),1.17
(t, J=7.2Hz, 3H).
Embodiment 2
Reaction equation is with embodiment 1, and specific operation process is as follows:
Under room temperature, to appropriate organic solvent (Isosorbide-5-Nitrae-dioxane and the polyethylene glycol 200 (PEG-200) for volume ratio 1:2
Mixture) in, add formula (II) compound described in formula (I) compound, 120mmol described in 100mmol, 8mmol catalyst double
(n-butyl cyclopentadienyl) zirconium dichloride, 10mmol alkali 1,4-diazabicylo [2.2.2] octane (DABCO), 15mmol help
Agent is (for 3mmol tetraphenylporphyrin and 12mmol copper trifluoromethanesulfcomposite (Cu (OTf)2) mixture) and 5mmol activator N-sulphur
Acid butyl pyridinium p-toluenesulfonate, is then warming up to 70 DEG C under stirring, and stirring reaction 10 hours at such a temperature；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate, to neutral, then fully shakes with deionized water
Swinging, add petroleum ether extraction 2-3 time, merge organic facies, concentrating under reduced pressure, gained residue crosses silica gel flash column chromatography, with body
The mixed liquor amassing the acetone than 1:3 and chloroform is rinsed, thus obtains described formula (III) compound, and productivity is 92.4%.
Characterize data consistent with Example 1.
Embodiment 3
Reaction equation is with embodiment 1, and specific operation process is as follows:
Under room temperature, to appropriate organic solvent (Isosorbide-5-Nitrae-dioxane and the polyethylene glycol 200 (PEG-200) for volume ratio 1:2
Mixture) in, add formula (II) compound described in formula (I) compound, 180mmol described in 100mmol, 4mmol catalyst double
(n-butyl cyclopentadienyl) zirconium dichloride, 20mmol alkali 1,4-diazabicylo [2.2.2] octane (DABCO), 8mmol auxiliary agent
(for 2mmol tetraphenylporphyrin and 6mmol copper trifluoromethanesulfcomposite (Cu (OTf)2) mixture) and 10mmol activator N-sulfonic acid
Butyl-pyridinium tosilate, is then warming up to 90 DEG C under stirring, and stirring reaction 7 hours at such a temperature；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate, to neutral, then fully shakes with deionized water
Swinging, add petroleum ether extraction 2-3 time, merge organic facies, concentrating under reduced pressure, gained residue crosses silica gel flash column chromatography, with body
The mixed liquor amassing the acetone than 1:3 and chloroform is rinsed, thus obtains described formula (III) compound, and productivity is 92.9%.
Characterize data consistent with Example 1.
From above-described embodiment 1-3, especially compared with the another piece patent application applied on the same day, when the synthesis of the present invention
When method adds activator, the productivity of product can be significantly increased.
Following repeat embodiment 1-3 is tested, to investigate the impact for end reaction effect of the different factors.
Embodiment 4-12
Embodiment 4-6: except double for catalyst (n-butyl cyclopentadienyl) zirconium dichlorides are replaced with double (cyclopentadienyl group)
Outside zirconium dichloride, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 4-6.
Embodiment 7-9: in addition to double for catalyst (n-butyl cyclopentadienyl) zirconium dichlorides are replaced with bis cyclopentadienyl zirconium dichloride, its
Its operation is the most constant, thus repeats to implement embodiment 1-4, sequentially obtains embodiment 7-9.
Embodiment 10-12: except double for catalyst (n-butyl cyclopentadienyl) zirconium dichlorides are replaced with hexafluoroacetylacetone
Outside zirconium, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 10-12.
Result see table 1.
Table 1
As can be seen here, double (n-butyl cyclopentadienyl) zirconium dichloride has best catalytic effect, other catalyst
Effect is all significantly reduced, even if double (cyclopentadienyl group) zirconium dichlorides similar with its structure.
Embodiment 13-27
Embodiment 13-15: except alkali DABCO replaces with 1, outward, other grasps 8-diazabicylo 11 carbon-7-alkene (DBU)
Make the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 13-15.
Embodiment 16-18: except alkali DABCO is replaced with 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene (TBD) outward, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 16-18.
Embodiment 19-21: in addition to alkali DABCO is replaced with NaOH, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, sequentially obtains embodiment 19-21.
Embodiment 22-24: in addition to alkali DABCO is replaced with potassium tert-butoxide, other operation is the most constant, thus repeats to implement
Embodiment 1-3, sequentially obtains embodiment 22-24.
Embodiment 25-27: in addition to alkali DABCO is replaced with dimethylamino naphthyridine (DMPA), other operation is the most constant, thus
Repeat to implement embodiment 1-3, sequentially obtain embodiment 25-27.
Result see table 2.
Table 2
As can be seen here, in all of alkali, DABCO has best effect, and other alkali all causes productivity to have significantly fall
Low, especially DMPA and TBD, this proves that the kind of alkali selects to be unpredictable.
Embodiment 28-36
Embodiment 28-30: in addition to auxiliary agent is replaced with the one-component tetraphenylporphyrin of original two kinds of total consumptions of component, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 28-30.
Embodiment 31-33: except the one-component copper trifluoromethanesulfcomposite (Cu that auxiliary agent is replaced with original two kinds of total consumptions of component
(OTf)2) outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 31-33.
Embodiment 34-36: in addition to being omitted by auxiliary agent, other operation is the most constant, thus repeats to implement embodiment 1-
3, sequentially obtain embodiment 34-36.
Result see table 3.
Table 3
As can be seen here, when using any one-component as auxiliary agent, productivity is significantly reduced, the most only
Use Cu (OTf)2Time, productivity is reduced to 63.3-64.2%.And more it is surprising that when not making used additives, productivity is on the contrary
There is 70.5-71.4%, be higher than embodiment 31-33 and simply use Cu (OTf)2Time productivity, this prove Cu (OTf)2Do not play
Any improve effect.And as Cu (OTf)2When being applied in combination with tetraphenylporphyrin, then achieve the excellent productivity of embodiment 1-3,
This proof has played beyond thought synergy and mutual promoting action between the two.
Embodiment 37-43
In addition to organic solvent is replaced with following one-component, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, obtains embodiment 37-43, and the organic solvent, embodiment corresponding relation and the products collection efficiency that are used see table 4.
Table 4
As can be seen here, when using single organic solvent, productivity the most significantly lower than uses Isosorbide-5-Nitrae-dioxane and PEG-
Productivity during 200 mixture, this proves that the kind of organic solvent has a certain impact for reaction process.
Embodiment 44-46
In addition to being omitted by activator N-sulfonic acid butyl-pyridinium tosilate therein, other operation is the most constant,
Thus repeat to implement embodiment 1-3, sequentially obtaining embodiment 44-46, result see table 5.
Table 5
As can be seen here, when not using this activator, the productivity of product has had significant reduction, and this proves N-sulfonic acid butyl
The use of pyridinium p-toluenesulfonate, can significantly improve reactivity, promotes that reaction forward is carried out, thus achieves excellence
Technique effect.
In sum, the invention provides the synthetic method of a kind of sulfenamide compounds, described method uses specific
Compound of reaction, and by catalyst, alkali, auxiliary agent, organic solvent and the combined selection of activator, such that it is able to high yield obtains
To purpose product, the synthesis for this compounds provides brand-new path, has actual application value widely.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, the present invention can be made respectively by those skilled in the art
Planting change, amendment and/or modification, all these equivalent form of value falls within the guarantor that the application appended claims is limited equally
Within the scope of protecting.
Claims (10)
1. a synthetic method for sulfenamide compounds shown in lower formula (III), described method includes: in organic solvent,
In the presence of catalyst, alkali, auxiliary agent and activator, lower formula (I) compound and lower formula (II) compound react, reaction knot
Shu Houjing post processing, thus obtain described formula (III) compound,
R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen.
2. synthetic method as claimed in claim 1, it is characterised in that: described catalyst is double (cyclopentadienyl group) dichloride
Any one in zirconium, bis cyclopentadienyl zirconium dichloride, double (n-butyl cyclopentadienyl) zirconium dichloride or hexafluoroacetylacetone zirconium, most preferably
For double (n-butyl cyclopentadienyl) zirconium dichloride.
3. synthetic method as claimed in claim 1 or 2, it is characterised in that: described alkali is 1,8-diazabicylo 11 carbon-7-
Alkene (DBU), 1,4-diazabicylo [2.2.2] octane (DABCO), 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene (TBD),
Any one in NaOH, potassium tert-butoxide or dimethylamino naphthyridine (DMPA), most preferably Isosorbide-5-Nitrae-diazabicylo [2.2.2] is pungent
Alkane (DABCO).
4. the synthetic method as described in any one of claim 1-3, it is characterised in that: described auxiliary agent is tetraphenylporphyrin and trifluoro
Copper methane sulfonate (Cu (OTf)2) mixture, wherein tetraphenylporphyrin and copper trifluoromethanesulfcomposite (Cu (OTf)2) mol ratio be 1:
3-4。
5. the synthetic method as described in any one of claim 1-4, it is characterised in that: described activator is N-sulfonic acid butyl-pyridinium
Tosilate.
6. the synthetic method as described in any one of claim 1-5, it is characterised in that: described formula (I) compound is changed with formula (II)
The mol ratio of compound is 1:1.2-1.8.
7. the synthetic method as described in any one of claim 1-6, it is characterised in that: described formula (I) compound and catalyst
Mol ratio is 1:0.04-0.08.
8. the synthetic method as described in any one of claim 1-7, it is characterised in that: described formula (I) compound and alkali mole
Ratio is 1:0.1-0.2.
9. the synthetic method as described in any one of claim 1-8, it is characterised in that: described formula (I) compound rubs with auxiliary agent
That ratio is 1:0.08-0.15.
10. the synthetic method as described in any one of claim 1-9, it is characterised in that: described formula (I) compound and activator
Mol ratio is 1:0.05-0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610496568.6A CN106045887B (en) | 2016-06-28 | 2016-06-28 | A kind of synthetic method of N- ethyls sulfenamide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610496568.6A CN106045887B (en) | 2016-06-28 | 2016-06-28 | A kind of synthetic method of N- ethyls sulfenamide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106045887A true CN106045887A (en) | 2016-10-26 |
| CN106045887B CN106045887B (en) | 2018-08-31 |
Family
ID=57166192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610496568.6A Expired - Fee Related CN106045887B (en) | 2016-06-28 | 2016-06-28 | A kind of synthetic method of N- ethyls sulfenamide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106045887B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520400A (en) * | 1947-11-03 | 1950-08-29 | Phillips Petroleum Co | Production of sulfenamides |
| US2671804A (en) * | 1948-12-28 | 1954-03-09 | Phillips Petroleum Co | Preparation and use of alkylene polyamine sulfenamides and thiosulefnamides |
| US3412144A (en) * | 1965-10-04 | 1968-11-19 | Dow Chemical Co | Process for producing sulfenamides |
| EP0016590A1 (en) * | 1979-03-07 | 1980-10-01 | The Regents Of The University Of California | N-Sulfinyl carbamates, their use as pesticides, pesticidal compositions containing them, methods of producing them and halosulfinyl carbamates formed during their production |
| US4350699A (en) * | 1981-03-30 | 1982-09-21 | The Regents Of The University Of California | Pyridylalkoxysulfinyl derivatives of carbamate esters |
| JP2000095751A (en) * | 1998-09-18 | 2000-04-04 | Agency Of Ind Science & Technol | Sulfenamide compound and its production |
| CN102307889A (en) * | 2008-12-23 | 2012-01-04 | 集润德斯股份公司 | Sulfurizing reagents and their use for oligonucleotides synthesis |
| CN105348159A (en) * | 2015-11-16 | 2016-02-24 | 河南理工大学 | Lead compound sulfo-methomyl and synthesis method thereof |
-
2016
- 2016-06-28 CN CN201610496568.6A patent/CN106045887B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520400A (en) * | 1947-11-03 | 1950-08-29 | Phillips Petroleum Co | Production of sulfenamides |
| US2671804A (en) * | 1948-12-28 | 1954-03-09 | Phillips Petroleum Co | Preparation and use of alkylene polyamine sulfenamides and thiosulefnamides |
| US3412144A (en) * | 1965-10-04 | 1968-11-19 | Dow Chemical Co | Process for producing sulfenamides |
| EP0016590A1 (en) * | 1979-03-07 | 1980-10-01 | The Regents Of The University Of California | N-Sulfinyl carbamates, their use as pesticides, pesticidal compositions containing them, methods of producing them and halosulfinyl carbamates formed during their production |
| US4350699A (en) * | 1981-03-30 | 1982-09-21 | The Regents Of The University Of California | Pyridylalkoxysulfinyl derivatives of carbamate esters |
| JP2000095751A (en) * | 1998-09-18 | 2000-04-04 | Agency Of Ind Science & Technol | Sulfenamide compound and its production |
| CN102307889A (en) * | 2008-12-23 | 2012-01-04 | 集润德斯股份公司 | Sulfurizing reagents and their use for oligonucleotides synthesis |
| CN105348159A (en) * | 2015-11-16 | 2016-02-24 | 河南理工大学 | Lead compound sulfo-methomyl and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHAN LEE等: "Copper-Catalyzed Synthesis of N-Formyl/Acylsulfenamides and -thiosulfonamides", 《EUR. J. ORG. CHEM.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106045887B (en) | 2018-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103224436A (en) | Preparation method of o-amino diaryl ketone compound | |
| CN107118215B (en) | A kind of preparation method for treating breast cancer medicines Rui Boxini intermediate | |
| CN106045887A (en) | Synthesis method of N-ethylsulfenamide compounds | |
| Goel et al. | Regioselective synthesis of functionally congested biaryls through a novel C–C bond formation reaction | |
| CN104016969A (en) | N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-substituted 1,2,3-triazole derivative | |
| CN106146364A (en) | A kind of synthetic method of sulfenamide compounds | |
| CN104803912B (en) | A kind of synthetic method of medicine intermediate quinoline compound | |
| CN110520411A (en) | The manufacturing method of pyridine compounds | |
| CN105461633A (en) | Enzalutamide preparation method | |
| CN105085320B (en) | Synthesis method of dicyano substituted biphenyl compounds | |
| CN105037081B (en) | A kind of trifluoromethylation method of xenyl olefin(e) compound | |
| UA88992C2 (en) | Process for the production of carboxanilides | |
| CN103694264B (en) | A kind of Sulfydryl nitrogen heterocyclic compound and preparation method thereof | |
| CN105481768A (en) | Synthetic method for drug intermediate diaryl ketone compound | |
| WO2008087736A1 (en) | Process for producing aromatic amine having aralkyloxy or heteroaralkyloxy group | |
| CN106045916A (en) | Synthesis method for imidazolone compound | |
| CN109232333A (en) | A kind of method that benzenesulfinic acid sodium salt synthesizes benzene sulfonyl olefinic amine compound without metal catalytic with triethylamine | |
| Patel et al. | Synthesis of indenoquinolinone through aryne-mediated Pd (II)-catalysed remote C–H activation | |
| CN105111116B (en) | A kind of process for catalytic synthesis of aryl thioether compound | |
| CN107663165A (en) | The new method that a kind of C H bond activations of the positions of indoles C 3 are efficiently esterified | |
| CN104628547B (en) | A kind of synthetic method of medicine intermediate difluoromethoxy based compound | |
| CN103333092B (en) | Synthesis method of 1-thiophenyl-2-isonaphthol compound | |
| CN105130983A (en) | Synthesis method for medical intermediate pyrazolopyridine compound | |
| CN106083729A (en) | A kind of synthetic method of benzimidazoles compound | |
| CN104529854B (en) | A kind of synthetic method of substituted azetidine class pharmaceutical intermediate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180723 Address after: 224600 Yancheng City City, Jiangsu province Chan Shui Kong County chemical industry concentrated area Applicant after: Jiangsu Zhijiang Chemical Co., Ltd. Address before: 311605 171 Jiande, Zhejiang, Hangzhou Applicant before: Fang Meilan |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180831 Termination date: 20190628 |