CN101535247B - Allylic polysulfanes - Google Patents

Abstract

Diallylic polysulfides (polysulfanes) are provided with sulfur chain lengths of 9 to 22. Also provided are bis(2-methyl-2-propenyl) polysulfides with sulfur chain lengths of 3 to 22. Also provided are 2-substituted bis(2-propenyl) polysulfides with sulfur chain lengths of 3 to 20. Also provided are the 2-cycloalken-1-yl polysulfides, 2-cyclohexen-1-yl polysulfides and 2-cyclopenten-1-yl polysulfides, with sulfur chain lengths of 3 to 20. Also provided are processes for extending the sulfur chain length of diallylic polysulfides and 2-substituted analogues thereof and allyl methyl polysulfides by bringing such compounds into contact with elemental sulfur and heating, or by mixing with molten sulfur.

Description

Allylic polysulfanes

Technical field

The analogue that the present invention relates to new diallylic polysulfanes (polysulfanes) and replace; For the preparation of the method for such compound; With the method for the sulphur chain length for extending described polysulfanes.

Background technology

Find diallyl polysulfide (polysulfanes: DASn, wherein n >=2) and derivative is natural is present in such as garlic oil (distilled oil of garlic), and find that it is for many technical fields, such as, as sterilant.The biological activity of known diallyl polysulfide changes with sulphur chain length, and the molecule long compared with long-chain demonstrates the activity (1) of enhancing usually.In the family of naturally occurring diallyl polysulfide, not there is the molecule more than eight sulphur atoms.But, expect that these materials will find huge potential, and demonstrate or selectable character that strengthen than known diallyl polysulfide.

As the mark of the potential application of diallyl polysulfide, the example of some Application Areass is followingly to provide with reference to other open source literature and patent application:

DAS2 and DAS3 (diallyl disulfide and diallyl trisulfide) can be used as the nematocides controlling pine wood nematodes class, and environment is free from side effects, described side effect such as reduce beneficial organisms population, improved and developed by the imbalance of the toxicology of the ecosystem tolerance and the induction toxicity (2) to the mankind and domestic animal by degraded and resistance, described toxicology imbalance can impel outburst latent insect infestations; DAS2-DAS7 (diallyl disulfide is to diallyl heptasulfide) can be used as sterilant, miticide, virucide, mycocide and plant-growth regulator (3,4); Diallyl polysulfide can be used as stablizer for unsaturated compound and polymerization retarder, and is used as antioxidant component (5); They can be used as the sterilant (6-8) of foliage application and other agricultural application with as tickicide (9); DAS2-DAS4 (diallyl disulfide is to diallyl tetrasulfide) prevents pine tree-wilt disease (10) by the larva controlling pine wood nematode (Bursaphelenchus xylophilus); They can be used as plant dormancy-inhibitor to accelerate sprout (11); Diallyl polysulfide can be used as the optical material strengthening specific refractory power, is used as extreme-pressure additive and the lubricating oil compound of automotive transmission, and is used as the protection ionogen (12) of lithium cell; They can be used as without amine sanitas (13); They can be used as therapeutical agent (14) with the form of cyclodextrin inclusion compound; DAS3-DAS7 can be used as mycocide and lipid peroxidation inhibitor (15); Diallyl polysulfide can be used as food preservatives and browning inhibitor (16).

Also diallyl trisulfide and the tetrasulfide purposes as microbiotic, biocide, antithrombotic agent, parasiticide, apoptosis-inductor and antineoplastic agent, anti-angiogenic agent and the compound as the toxicity providing Cadmium resistance and other toxic metal to cause is reported in scientific literature.Can find out that range of application is very wide, the diallyl polysulfide of higher chain length will be useful in many technical fields.

Method for the preparation of diallyl trisulfide, tetrasulfide and pentasulfide is known (17-24).

Summary of the invention

Therefore, in first, the invention provides the compound of following formula:

Wherein n is 3 to 22; And R ¹be selected from: hydrogen; Methyl; Phenyl; Ethoxycarbonyl; Methoxycarbonyl; Carboxyl; Methylol; Trimethylsilylmethyl; Short-chain alkyl; Chlorine and fluorine; Condition is when n is 3 to 8, R ¹be not hydrogen.

Especially, the invention provides such compound, wherein n be more than or equal to 4 or 5 or 6, or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18, n is for being less than or equal to 21,20 or 19 simultaneously.Such as, n is 4 to 22 or 5 to 22 or 6 to 22 etc.; Or 4 to 21 or 5 to 21 or 6 to 21 or 7 to 21 etc.; Or 4 to 20 or 5 to 20 or 6 to 20 or 7 to 20 etc.

Especially, also preferably when n is 3 to 9, or 3 to 10, or even 3 to 11 time, R ¹be not hydrogen.

In this group, described short-chain alkyl preferably includes the alkyl with 2,3 or 4 carbon atoms.

In second, the invention provides the compound of following formula:

Wherein n is 9 to 22.Especially, the invention provides such compound, wherein n is more than or equal to 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18, and n is for being less than or equal to 21,20 or 19 simultaneously.Such as, n is 4 to 22 or 5 to 22 or 6 to 22 etc.; Or 4 to 21 or 5 to 21 or 6 to 21 or 7 to 21 etc.; Or 4 to 20 or 5 to 20 or 6 to 20 or 7 to 20 etc.

In the 3rd, the present invention also provides the compound of following formula:

Wherein n is 3 to 22.Especially, the invention provides such compound, wherein n is more than or equal to 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18, and n is for being less than or equal to 21,20 or 19 simultaneously.Such as, n is 4 to 22 or 5 to 22 or 6 to 22 etc.; Or 4 to 21 or 5 to 21 or 6 to 21 or 7 to 21 etc.; Or 4 to 20 or 5 to 20 or 6 to 20 or 7 to 20 etc.

In the 4th, the present invention also provides a kind of method of the sulphur chain length for extending diallylic polysulf, and described diallylic polysulf is selected from:

Two (2-propenyl) polysulfide; With

Two (2-propenyl) polysulfide that 2-replaces;

It comprises the described diallylic polysulf of mixing and elementary sulfur, and heats this mixture to the step higher than 50 degree celsius temperature.The increase of speed of reaction and yield with temperature and increasing, and increase significantly, therefore, particularly preferably is and this mixture is heated above 60 DEG C or higher than 70 DEG C or higher than 80 DEG C, or most preferably higher than the temperature of 90 DEG C.In particularly preferred embodiments, described mixture is heated to elementary sulfur fusing point (115-120 DEG C) or close to this fusing point or even higher than the temperature of this fusing point.In particularly preferred embodiments, described method comprises by the reaction with elementary sulfur, and the sulphur chain length extending diallyl disulfide comprises the diallyl polysulfide of 3 to 8 sulphur atoms with preparation.

In the 5th, the present invention also provides a kind of method of the sulphur chain length for extending diallylic polysulf, and described diallylic polysulf is selected from: two (2-propenyl) polysulfide; With two (2-propenyl) polysulfide that 2-replaces; Described method comprises the step of the described diallylic polysulf of mixing and melting sulphur.

Within in described 4th and the 5th, preferably described diallylic polysulf comprises diallyl disulfide, i.e. Allyl disulfide compound.

In 4th or the 5th of the present invention, be particularly preferably that the diallylic polysulf of so preparation comprises the polysulfide having and be less than 22 sulphur atoms.

In the 6th, the present invention also provides the compound of following formula:

Wherein R ¹be selected from:

Phenyl;

Ethoxycarbonyl;

Methoxycarbonyl;

Carboxyl;

Methylol;

Short-chain alkyl;

Trimethylsilylmethyl;

Chlorine; With

Fluorine;

Be 3 to 20 with n.

Within these groups, described short-chain alkyl preferably includes the alkyl with 2,3 or 4 carbon atoms.

In the 7th, the present invention also provides the compound of following formula:

Wherein n is 3 to 20.

In preferred embodiment, n is 3 to 18.

The present invention also provides the compound of following formula:

Wherein n is 3 to 20.

In preferred embodiment, n is 3 to 18.

In the 8th, the present invention also provides a kind of for extending allyl methyl polysulfides (MeS _ncH ₂cH=CH ₂) the method for sulphur chain length, it comprises the described allyl methyl polysulfides of mixing and elementary sulfur, and heats this mixture to the step higher than 50 degree celsius temperature.The increase of speed of reaction and yield with temperature and increasing, and increase significantly, therefore, particularly preferably is and this mixture is heated above 60 DEG C or higher than 70 DEG C or higher than 80 DEG C, or most preferably higher than the temperature of 90 DEG C.In particularly preferred embodiments, described mixture is heated to elementary sulfur fusing point or close to this fusing point or even higher than the temperature of this fusing point.

In the 9th, the present invention also provides a kind of for extending allyl methyl polysulfides (MeS _ncH ₂cH=CH ₂) the method for sulphur chain length, it comprises the step of the described allyl methyl polysulfides of mixing and molten sulfur.

In any one method described in described 4th, the 5th, the 8th or the 9th, particularly preferably described reaction is not having to carry out under other solvent substantially.

Also in any one method described in described 4th, the 5th, the 8th or the 9th, the independent polysulfanes of so preparation can be obtained by separation method, described separation method is preparative high performance liquid chromatography (HPLC) such as, can be isolated into the mixture of lower polysulfides and the mixture of higher polysulfides by obtaining with methyl alcohol or alcohol extraction simultaneously.(the S chain length such as, had is for being greater than about S for described senior polysulfanes ₇) be insoluble to alcohol, particularly methyl alcohol.Alternatively, as required, the mixture of the sulphur chain length homologue of so preparation can combinationally use.

Also in any one method described in described 4th, the 5th, the 8th or the 9th, single homologue starting raw material can be used (such as, such as diallyl disulfide), or the mixture be pre-existing in can be used, such as garlic (Allium sativum) natural extract, or distillation thing.

Of the present invention significantly and the feature of uniqueness comprise needs very short heat-up time high reaction rate, good productive rate, avoid solvent, do not have the smell of higher polysulfides and formation to comprise the polysulfide of 20 chain sulphur atoms at the most, such as All ₂s _n, wherein n any integer of equaling 1 to 20, described diallylic higher polysulfides is new material, (above-mentioned All unknown in the past ₂s ₈, when parent diallyl system), it is nonpolar, dissolves in chloroform and related solvents, but is insoluble to alcohol, different from rudimentary diallylic polysulf.

The explanation of reference or any suitable combination by accompanying drawing, Compounds and methods for is also included within scope of the present invention as described herein substantially.

Embodiment

Diallyl disulfide is added in the sulphur liquefied under its temperature of fusion of 115-120 DEG C, and strong stirring.Diallyl disulfide and sulphur are (as S ₈) ratio can be 1: 0.25 to 1: 2, although can use than regulation those smaller or greater ratios.Work as disulphide: the ratio of sulphur reduces (such as, S ₈> disulphide) time, at 120 DEG C, speed of reaction can be faster.As long as five minutes just there will be a large amount of reaction, and completed in fact after two hours.At 115 DEG C, the reaction of diallyl disulfide and liquid sulfur is slowed down.Higher than at the temperature of 120 DEG C, described reaction is faster, but occurs decomposing, as shown in blackening as remarkable in reaction mixture.

Saturated disulphide, such as dibenzyldisulfide, sulphur lacks allyl group, and described reaction has been slowed down in fact, it is believed that and has occurred different mechanism.Slower in fact than diallyl disulfide of the reaction of diallyl sulfide and liquid sulfur, so, also must relate to different mechanism in this case.The diallylic disulphide replaced, such as dimethallyl based bisulfide, also reacts with sulphur, and two-cinnamyl disulphide such as (PhCH=CHCH ₂s) ₂do not react with sulphur, wherein at the sulfo-sulfoxide intermediate such as CH of hypothesis ₂=CHCH (Ph) S (S) CH ₂conjugation in CH=CHPh has been destroyed.The diallylic disulphide that any 2-replaces all will carry out described reaction, two (2-phenyl-2-propenyl), two (2-ethoxycarbonyl-2-propenyl), two (2-methoxycarbonyl-2-propenyl), two (2-carboxyl-2-propenyl), two (2-methylol-2-propenyl), two (2-chloro-2-propene bases), two (the fluoro-2-propenyl of 2-) or two (2-trimethylsilylmethyl) disulphide.Be 2-cyclenes-1-based bisulfide by other diallylic disulphide carrying out described reaction, such as 2-tetrahydrobenzene-1-base and 2-cyclopentenes-1-based bisulfide, it can be considered to the dibasic diallylic disulphide of 1,3-.In often kind of said circumstances, starting raw material can be the disulphide mentioned, S ₈amount be 0.25 to 2 equivalent, reaction conditions will comprise heating 115 DEG C to 120 DEG C three hours at the most.Top condition is comprised, S although above-mentioned ₈proportional range and Heating temperature and heating period can be wider than those description.

Described reaction is believed to comprise diallylic disulphide such as All-SS-All and is isomerizated into sulfo-sulfoxide isomer, such as All ₂s ⁺-S ^-(25).Sulfo-sulfoxide group is polar group, and end sulphur is with negative charge (25,26), and this electronegative sulphur under fire and open loop cyclooctasulfur according to inferring, S ₈, obtain ionic species such as All ₂s ⁺-S ₈-S ^-, it is attacked (possibly via S by electronegative sulphur _n2 ' process) initial diallyl disulfide, obtain the product of final sulfo-allylation, such as All ₂s ⁺-S ₈-SAll, then, it loses the allyl group on the sulphur of positive sulfo-sulfonium (thiosulfonium) of two basic change by attacking nucleophilic reagent, obtain AllS-S ₈the product of-SAll type.Then, this product can lose a large amount of sulphur atom, as small molecules S _n.This whole process is completely different from the significant reaction ground of saturated disulphide and cyclooctasulfur, and the reaction of described the latter only occurs at relatively high temperatures, and the diradical such as S that the free radical open loop being considered to relate to cyclooctasulfur obtains ₈with the free radical that the free radical cracking of disulphide obtains, such as RS ^*(27).Relate to the comparatively high temps of the reaction of saturated disulphide and free radical character by the formation of reactive higher polysulfides unstable for restriction, by analysed by reverse phase HPLC and mass spectroscopy susceptible of proof, it is present in our research.For the same reason, diallyl sulfide All ₂s does not promote S ₈the polarity S of open loop ⁺-S " key.Therefore, All ₂the considerably less nucleophilic sulfide sulfur of S is to S ₈attack also will need stronger higher temperature conditions (28).When heating the liquid S that mol ratio is 0.625 to 1 at 120 DEG C ₈and All ₂s two is constantly little, does not observe reaction.

The diallyl disulfide of embodiment 1:1: 1 mol ratio and elementary sulfur are (as S ₈)

Sublimed sulphur (S will be comprised ₈, 0.640g, 2.50mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once diallyl disulfide (0.365g, 2.50mmol) is joined in the liquid of magnetic stirring.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At multiple time point, such as 5 minutes, 30 minutes, 1 hour, 1.5 hours and 2 hours, from this reaction mixture, take out a small amount of sample for analyzing.The sample of taking-up is dissolved in CDCl ₃in, to carry out NMR and analysed by reverse phase HPLC to same sample.When needed, can directly use remaining material, or by extracting and separating methyl alcohol-or ethanol-soluble fraction from alcohol insoluble matter resistates, then, be dissolved in chloroform and be used for further use.By C18 HPLC (85: 15 MeOH: H ₂o) to being dissolved in CHCl ₃in the analysis of sample demonstrate the peak at one group of smooth interval, correspond to (CH ₂=CHCH ₂) ₂s _n, n=2-20, with unreacted S ₈, as shown in appended HPLC trace.Diode-array the UV spectrum at each HPLC peak confirms " family " relation of described mixture member.Our observations is studied consistent with the HPLC of dialkyl polysulfide family, in wherein said chain sulphur atom number and according to retention time calculate capacity factor natural logarithm between there is linear relationship (29).The 1NMR spectrum of starting raw material (Fig. 1) and 1 hr sample (Fig. 2) demonstrate CH more clearlyly ₂-S proton occurs bimodal at δ 3.62 and 3.60, and it is All ₂s _n, the feature of n>=5.

Due to the CH that deshielded gradually ₂s _nproton, the NMR of diallyl polysulfide analyzes and can be used for quantitative monosulphide, disulphide, trisulphide, the pentasulfide of tetrasulfide and mixing and the relative quantity (30) of more higher polysulfides.HPLC is analyzed as follows:

Come comfortable 500MHz's ¹h NMR analyzes the display of (relative to interior mark), and to generate the data of the percentage ratio of often kind of homologue in time as follows:

The diallyl disulfide of embodiment 2:2: 1 mole and elementary sulfur are (as S ₈) mixture

Sublimed sulphur (S will be comprised ₈, 1.28g, 5mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once diallyl disulfide (1.48g, 10.1mmol) is joined in the liquid of magnetic stirring.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At 120 DEG C, continue stirring one hour.With ¹h NMR analyzes aliquots containig, CH ₂-S proton is at δ 3.09/3.07 (8%All ₂s), δ 3.33/3.31 (9%All ₂s ₂), δ 3.50/3.48 (12%All ₂s ₃), δ 3.58/3.56 (16%All ₂s ₄), δ 3.62/3.60 (54%All ₂s _n), n>=5 demonstrate bimodal.

By 0.1081g part reaction product with ethanol (5 × 1mL) washing, until ethanolic extract becomes colourless.From resistates, remove trace solvent, obtain the odorless of 0.0291g (productive rate 27%), sticky yellow liquid, it is characterized in that All ₂s _n, NMR and HPLC (see Fig. 3) of n=8 to 20 demonstrates the ethanol-insoluble fraction of reaction product.Therefore, ¹h NMR spectrum demonstrates CH ₂-S proton is bimodal δ's 3.62 and 3.60, and it is All ₂s _n, the feature of n>=5.HPLC analysis demonstrates following approximate composition, and (the UV optical extinction coefficient changed for system does not correct, and wherein said detector is more responsive to higher polysulfides; Therefore, following result enhances the level of higher polysulfides): All ₂s ₄(tr), All ₂s ₅(1%), All ₂s ₆(2%), All ₂s ₇(4%), All ₂s ₈(8%), All ₂s ₉(11%), All ₂s ₁₀(13%), All ₂s ₁₁(13%), All ₂s ₁₂(11%), All ₂s ₁₃(9%), All ₂s ₁₄(7%), All ₂s ₁₅(6%), All ₂s ₁₆(4%), All ₂s ₁₇(3%), All ₂s ₁₈(3%), All ₂s ₁₉(2%), All ₂s ₂₀(1%), All ₂s ₂₁(tr), All ₂s ₂₂(tr); The peak of elementary sulfur appears at All ₂s ₇and All ₂s ₈peak between.

In the reaction product of initial 0.1081g, 0.0291g is that ethanol is insoluble, and 0.0703g is ethanol soluble.Difference between the total amount 0.0994g of ethanol soluble and the insoluble fraction of ethanol and primitive reaction product 0.1081g represents volatile compound (such as diallyl sulfide) and loses in operation and ethanol evaporation.The rate of recovery is 92.0%.Dense ethanol extraction corresponds to All ₂s _n, n=1 to 9, HPLC analysis demonstrates following approximate composition, and (the UV optical extinction coefficient changed for system does not correct, and wherein said detector is more responsive to higher polysulfides; Therefore, following result enhances the level of higher polysulfides): All ₂s ₂(2.3%), All ₂s ₃(8.6%), All ₂s ₄(17.3%), All ₂s ₅(28.5%), All ₂s ₆(23.7%), All ₂s ₇(11.9%), All ₂s ₈(5.3%), All ₂s ₉(2.3%). ¹the analysis of the eihanol soluble fraction of H NMR demonstrates 6.8%DAS2,15.0%DAS3,20.2%DAS4 and 58.0%DASn, n>=5.It is bimodal that the analysis of the insoluble fraction of ethanol demonstrates at 3.62/3.60, represents that DASn, n >=5 be the compound of unique existence.

According to the similar approach of above-mentioned alcohol extraction, extract the crude product of 0.1063g part with methyl alcohol (5 × 1mL), until methanol extract becomes colourless.Use the methyl alcohol in the resistates of rotatory evaporator removing methanol extract and methanol extraction, obtain the methanol soluble fraction of 0.0603 (G) and odorless, the aqueous resistates of sticky yellow of 0.0404g (38%).Total yield is 94.7%..With ¹the methanol soluble fraction that H NMR analyzes demonstrates 8.7%DAS2,20.1%DAS3,38.0%DAS4 and 33.2%DASn, n>=5.The analysis of the insoluble fraction of methyl alcohol is presented at the bimodal of 3.62/3.60, shows DASn, and n >=5 are unique compound existed.

For ethanol soluble extract, HPLC is analyzed as follows:

For the insoluble extract of ethanol, HPLC is analyzed as follows:

For methanol soluble extract, HPLC is analyzed as follows:

For insoluble methyl alcohol extract, HPLC is analyzed as follows:

The diallyl disulfide of embodiment 3:1: 1 mol ratio and elementary sulfur are (as S ₈) and internal standard

Sublimed sulphur (S will be comprised ₈, 0.640g, 2.50mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once by 4, the solution of 4 '-di-t-butyl phenylbenzene (0.0361g, 0.136mmol) in diallyl disulfide (0.365g, 2.50mmol) joins in the liquid of magnetic stirring.4,4 '-di-t-butyl phenylbenzene is as just the internal standard for analysis purposes.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At multiple time point, such as 5 minutes, 30 minutes, 1 hour, 1.5 hours and 2 hours, from this reaction mixture, take out a small amount of sample for analyzing.The sample of taking-up is dissolved in CDCl ₃in, to carry out NMR and analysed by reverse phase HPLC to same sample.When needed, can directly use remaining material, or by extracting and separating methyl alcohol-or ethanol-soluble fraction from alcohol insoluble matter resistates, then, be dissolved in chloroform and be used for further use.

Come comfortable 500MHz's ¹h NMR analyzes the display of (relative to internal standard), and to generate the representative data of the percentage ratio of often kind of homologue in time as follows:

After heating 2 hours, the total area of polysulfide fraction is reduced to 68% of original value continuously relative to internal standard, shows to lost some volatile matter.

The HPLC of 30 minutes aliquots containigs is analyzed as follows:

The diallyl disulfide of embodiment 4:1: 0.25 mol ratio and elementary sulfur are (as S ₈)

Sublimed sulphur (S will be comprised ₈, 0.25g, 0.977mmol) l0mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once diallyl disulfide (0.57g, 3.90mmol) is joined in the liquid of magnetic stirring.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At multiple time point, such as 0 minute, 30 minutes, 1 hour, 2 hours and 3 hours, from this reaction mixture, take out a small amount of sample for analyzing.The sample of taking-up is dissolved in CDCl ₃in, to carry out NMR and analysed by reverse phase HPLC to same sample.In different time points (as above) ¹h NMR is analyzed as follows:

The HPLC of three hours aliquots containigs is analyzed as follows:

The diallyl sulfide of embodiment 5:1: 0.6 mol ratio and elementary sulfur are (as S ₈)

Under these conditions, after 2 hours, the diallyl sulfide (bp 139-140 DEG C) of 1: 0.6 mol ratio and elementary sulfur are as S ₈mixture keep two-layer, there is no Indicator Reaction.Because this reaction conditions at the boiling point, may obtain conclusion thus: under the condition of diallyl disulfide, the reactivity of the sulphur of diallyl sulfide is not enough to open loop S ₈ring.

Two-(2-methacrylic) disulphide of embodiment 6:1: 1.1 mol ratios and elementary sulfur are (as S ₈) and internal standard

Sublimed sulphur (S will be comprised ₈, 0.640g, 2.50mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once by 4,4 '-di-t-butyl phenylbenzene (0.0308g, solution 0.116mmol) in two-(2-methacrylic) disulphide (0.415g, 2.38mmol) joins in the liquid of magnetic stirring.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At multiple time point, such as 5 minutes, 10 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 1.5 hours and 2 hours, from this reaction mixture, take out a small amount of sample for analyzing.The sample of taking-up is dissolved in CDCl ₃in, to carry out NMR and analysed by reverse phase HPLC to same sample.When needed, can directly use remaining material, or by extracting and separating methyl alcohol-or ethanol-solvable fraction from alcohol insoluble matter resistates, then, be dissolved in chloroform and be used for further use.Initial disulphide demonstrates at it ¹two CH in H NMR spectrum ₂sS proton is unimodal δ's 3.2638.After heating with sulphur, also find unimodal at δ 3.007 (monosulphide), 3.431 (trisulphides), 3.502 (tetrasulfides) and 3.537 (pentasulfide and more senior sulfide).After heating 30 minutes, HPLC analysis (see table) demonstrates the peak more than 20 equispaceds, two (2-methyl-2-propenyl) polysulfide family that the family that it represents and diallyl disulfide is formed is similar.

From ¹the data of the display higher homologue reaction process that H NMR analyzes are as follows:

^*s ₁=bis-(2-methacrylic) sulfide;

S ₂=bis-(2-methacrylic) disulphide;

S ₃=bis-(2-methacrylic) trisulphide; Deng

The data analyzed from the HPLC of 30 minutes samples are as follows:

The garlic oil of embodiment 7:1: 1.1 mol ratios and elementary sulfur are (as S ₈)

Sublimed sulphur (S will be comprised ₈, 0.6414g, 2.505mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once commercially available (0.4191g, based on diallyl trisulfide 2.35mmol) is joined in the liquid of magnetic stirring (garlic oil is the mixture of the diallyl polysulfide of about 80% and the allyl methyl polysulfides of 20%).In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.After 30 minutes, from this reaction mixture, take out a small amount of sample, and be dissolved in CDCl ₃in, by NMR and analysed by reverse phase HPLC.The HPLC of following display analyzes and shows to define a large amount of polysulfide, and it comprises and to have and those of DASn, n=7-19 have the compound of similar retention time.

CH ₂the NMR spectroscopic analysis of S proton shows to define diallyl polysulfide race and allyl group/methyl polysulfide race, MeS _ncH ₂cH=CH ₂, compared with 11% of initial garlic oil, the product of 65% has n>=5.CH ₃the NMR of S proton analyzes and shows compared with 16% of initial garlic oil, which form 62% there is CH ₃s _n, the family of the methallyl polysulfide of n>=5.

^*s ₁=diallyl sulfide; S ₂=allyl disulfide;

S ₃=diallyl trisulfide compound; Deng

Starting raw material (Fig. 4) and 0.5 hr sample (Fig. 5) ¹nMR spectrum demonstrate CH more clearlyly ₂in δ 3.62 and 3.60 bimodal, (it is All to-S proton ₂s _n, the feature of n>=5) size increase, the bimodal corresponding reduction of rudimentary S-chain length polysulfide.

Embodiment 8: at 120 DEG C, the 2-tetrahydrobenzene-1-based bisulfide of 1: 1 mol ratio and elementary sulfur are (as S ₈)

Sublimed sulphur (S will be comprised ₈, 0.256g, 1.00mmol) 10mL round-bottomed flask be placed in the oil bath being preheated to 120 DEG C.When all sulphur is all fused into clarification, lurid liquid, at once 2-tetrahydrobenzene-1-based bisulfide (0.226g, 1.00mmol) is joined in the liquid of magnetic stirring.In three minutes, the two-layer liquid mixture of initial muddiness becomes the clarification only with a liquid layer, uniform solution.At multiple time point, from this reaction mixture, within such as 5 minutes, 30 minutes, 1 hour and 2 hours, take out a small amount of sample for analyzing.The sample of taking-up is dissolved in CDCl ₃in, to carry out NMR and analysed by reverse phase HPLC to same sample.The HPLC of following list analyzes a series of peaks showing 18 sulphur atoms in chain for 2-tetrahydrobenzene-1-polysulfide.At it ¹in H NMR spectrum, 2-tetrahydrobenzene-1-based bisulfide demonstrates the multiplet at δ 3.48-3.51, and it can distribute to allylic CH-S proton.When heated, non-existent new broad peak in starting raw material is appeared at δ 3.88.This peak is inferred to be the allylic CH-S of 2-tetrahydrobenzene-1-polysulfide _nproton.According to the integration of several NMR spectrum, the time course that polysulfide is formed shows below:

The data analyzed from the HPLC of 1 hr sample are as follows:

At (tetrahydrobenzene-1-base) ₂s ₁₈stop HPLC behind peak to analyze, but analogize according to embodiment 2 and 3, expection has more higher homologue.

Embodiment 9: at 130 DEG C, the diallyl disulfide of 1: 0.2 mol ratio and elementary sulfur are (as S ₈)

By diallyl disulfide (20g; 0.14 mole) mix with Powdered sulphur (8g, 0.03 mole), and be heated 130 DEG C 10 minutes, then cool.Alcohol extraction is carried out to the mixture obtained, thus dissolves the long polysulfide of short chain.Analyze ethanolic extract by HPLC, obtain following result:

Embodiment 10: at 110 DEG C, the diallyl disulfide of 1: 0.2 mol ratio and elementary sulfur are (as S ₈)

By diallyl disulfide (20g; 0.14 mole) mix with Powdered sulphur (8g, 0.03 mole), and be heated 110 DEG C 10 minutes, then cool.Alcohol extraction is carried out to the mixture obtained, thus dissolves the long polysulfide of short chain.Analyze ethanolic extract by HPLC, obtain following result:

Embodiment 11: at 145 DEG C, the diallyl disulfide of 1: 0.4 mol ratio and elementary sulfur are (as S ₈)

By diallyl disulfide (20g; 0.14 mole) and powder sulphur (12g; 0.05 mole) mixing, and be heated to 145 DEG C 5 minutes, then cool.Alcohol extraction is carried out to the mixture obtained, thus dissolves the polysulfide of low chain length.Analyze ethanolic extract by HPLC, obtain following result:

Fig. 6 outlines the result of embodiment 9-11, and describes the effect of temperature of reaction to the spectrum of gained polysulfide.Can find out, temperature of reaction is change from 110 DEG C to 145 DEG C, and the spectrum of gained diallyl polysulfide moves to longer chain length.Therefore, use temperature the spectrum of chain length can be controlled.Under the lesser temps of embodiment 10, the unreacted DAS2 of residue fundamental quantity.

Embodiment 12: at 110 DEG C and afterwards at 140 DEG C, the diallyl disulfide of 1: 0.4 mol ratio and elementary sulfur are (as S ₈)

By diallyl disulfide (20g; 0.14 mole) and powder sulphur (16g; 0.06 mole) mixing, be heated to 110 DEG C, and keep 15 minutes in this temperature.Then, this reaction mixture is cooled, until occur that sulphur precipitates, then, reheat 140 DEG C, remain on this temperature 5 minutes, cool afterwards.Alcohol extraction is carried out to the mixture obtained, thus dissolves the polysulfide of low chain length.Analyze ethanolic extract by HPLC, obtain following result:

Can find out in this embodiment, remain considerably less unreacted DAS2 (peak area is less than 5%), with in embodiment 10 64% higher polysulfides compare, higher polysulfides (DAS4-DAS7) comprises the total peak area of 80%.In addition, the DAS4 concentration in embodiment 12 is almost DAS4 concentration high close to 1.5 times obtained in embodiment 10, and it causes due to reaction conditions.

Therefore, by utilizing such two kinds-temperature regime reaction, significant advantage can be obtained, described temperature regime reaction, that is, mix intitation reagents (elementary sulfur and diallyl polysulfide, such as DAS2, or the analogue of its 2-replacement); Be heated above the triple point of sulphur; This this mixture is remained on this temperature; Reduce temperature until observe sulphur and be settled out; With reheat this mixture to higher than the triple point of sulphur.

Term

DAS diallyl sulfide

DAS2 diallyl disulfide

DAS3 diallyl trisulfide

DAS4 diallyl tetrasulfide

DAS5 diallyl pentasulfide

DAS6 diallyl hexasulfide

DAS7 diallyl heptasulfide

DASn diallyl S _n

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Claims (8)

1., for extending a method for the sulphur chain length of diallylic polysulf, described diallylic polysulf is selected from:

Two (2-propenyl) polysulfide; With

Two (-2-the propenyl that 2-replaces) polysulfide;

Described method comprises mixing described diallyl polysulfide and elementary sulfur, and this mixture is heated to temperature higher than the step of 50 degrees Celsius.

2. method according to claim 1, the temperature of wherein said mixture be heated to elementary sulfur fusing point or higher than this fusing point.

3., according to the method for claim 1 or 2, wherein said diallylic polysulf comprises diallyl polysulfide.

4., for extending a method for the sulphur chain length of diallylic polysulf, described diallylic polysulf is selected from:

Two (2-propenyl) polysulfide; With

Two (-2-the propenyl that 2-replaces) polysulfide;

Described method comprises the step mixed with molten sulfur by described diallylic polysulf.

5. the method any one of claim 1 to 2, wherein said diallylic polysulf comprises the polysulfide having and be less than 22 sulphur atoms.

6. for extending an allyl methyl polysulfides, MeS _ncH ₂cH=CH ₂, the method for sulphur chain length, it comprises and being mixed with elementary sulfur by described allyl methyl polysulfides, and this mixture is heated above the step of the temperature of 50 degrees Celsius.

7. method according to claim 6, wherein heats fusing point that described mixture to temperature is elementary sulfur or higher than this fusing point.

8. for extending an allyl methyl polysulfides, MeS _ncH ₂cH=CH ₂, the method for sulphur chain length, it comprises the step mixed with molten sulfur by described allyl methyl polysulfides.