CN103739529A - Synthetic method of phenyl or substituted phenyl terminated long chain fatty thiol - Google Patents
Synthetic method of phenyl or substituted phenyl terminated long chain fatty thiol Download PDFInfo
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Abstract
The invention discloses a synthetic method of phenyl or substituted phenyl terminated long chain fatty thiol. The synthetic method comprises the following steps: firstly, by using (substituted) phenyl halide or (substituted) benzyl halide as a reactant, carrying out format coupling reaction with halo-terminated long chain fatty alcohol to obtain phenyl or substituted phenyl terminated long chain fatty alcohol; then, by using phenyl or substituted phenyl terminated long chain fatty alcohol as a raw material, reacting with a thiolation reagent thiourea to obtain phenyl or substituted phenyl terminated long chain fatty thiol. The yield in the first step of the synthetic method is above 82% and the yield in the second step is above 95%, and the purity of a final product is above 98.5%. The synthetic method has the advantages of mild conditions, simplicity in operation, simplicity and convenience in after-treatment, stable product quality, high preparation efficiency and environment-friendly process.
Description
Technical field
The present invention relates to a kind of synthetic method of fatty mercaptan, particularly relating to a kind of end is the synthetic method of the long-chain fat mercaptan of phenyl or substituted-phenyl.
Background technology
End phenyl or substituted-phenyl long-chain fat mercaptan are one of principal item of thio-alcohol self-assembled monolayer (SAMs), because of its have, molecular arrangement wide to choice of the substrates scope in order, the unique advantage such as high, the few surface defects of film even compact, thermodynamic stability, be widely used in various new or the traditional field such as MEMS (micro electro mechanical system), biochip, new functional materials, molecular device, metal protection, electrochemistry.
The structural formula of end phenyl or substituted-phenyl long-chain fat mercaptan is as follows:
Wherein, R is the substituting group on phenyl ring, can be C
1-4alkyl or alkoxyl group, phenyl, benzyl etc.; M represents substituent number on phenyl ring, is generally 0,1,2 or 3; N>=8, preferably 9～20.
Synthetic information report about end phenyl or substituted-phenyl long-chain fat mercaptan is less, and according to existing report data, its synthetic method mainly contains following four kinds.
Method one: take phenyl lithium or benzyl lithium is starting raw material, in two steps synthetic (Langmuir[J]. 2001,17,7364-7370; Langmuir[J]. 2003,19,9724-9729; J. Coll. Int. Sci.[J]. 2004,274,365-370; J. Angew. Chem. Int. Ed.[J]. 2011,50,7900-7905; Deng), first react with two ends halo long-chain fat alkane and make intermediate product end phenyl long-chain fat haloalkane, then through mercaptolation, obtain target product end phenyl or substituted-phenyl long-chain fat mercaptan with sulfhydrylization reagent (thiocarbamide or hexamethyl disilthiane).
Although the method synthesis step is few, total recovery low (approximately 10%), raw material be expensive, dangerous, be not easy to obtain, and especially the first step byproduct of reaction is many, and intermediate product separation difficulty, efficiency are low, and industrialization is difficult to be promoted.
Method two: take phenyl lithium or benzyl lithium is starting raw material, minute three steps synthetic (Langmuir[J]. 2001,17,7364-7370; J. Ad. Sci. Tech.[J]. 2010,24,2511-2529; DE 19547023A1; Deng), first make intermediate product 1 end phenyl or substituted-phenyl long-chain fat end alkene with end halo long-chain fat end alkene reaction, under causing, Diisopropyl azodicarboxylate (BNDI) makes intermediate product 2 end phenyl or substituted-phenyl long-chain fat mercaptan acetic ester with thioacetic acid (HSAc) again, finally by lithium aluminum hydride (LiAlH
4) reduction obtains target product end phenyl or substituted-phenyl long-chain fat mercaptan.
Although the method synthesis yield slightly high (approximately 50%), has equally raw material costliness, danger, is not easy to obtain, and operational condition requires the defects such as harsh.
Method three: the end of take is starting raw material to methoxy phenoxy long-chain fat haloalkane, minute three steps synthetic (Synthesis[J]. 1999, (6): 953-958; J. Bio. Med. Chem.[J]. 2002,10,3351-3359; Deng), first with phenylbenzene copper lithium (LiCuPh
2) reaction make intermediate 1 end to methoxy phenoxy long-chain fat alkylbenzene, then with boron tribromide (BBr
3) reaction makes intermediate 2 end phenyl long-chain fat haloalkanes, last and thiocarbamide obtains target product through mercaptolation.
The method total recovery slightly high (approximately 44%), but expensive raw material price and being not easy to obtain, be difficult to industrialization promotion.
Method four: take end halo long chain aliphatic alcohol, phenyl aldehyde is main starting raw material, through the synthetic target product of hydroxyl protection, phosphonium ylide preparation, phosphonium ylide reaction, reduction, hydroxyl deprotection, halo, sulfhydrylation seven steps reaction (J. Bio. Med. Chem.[J]. 2002,10,3351-3359; Deng).
Although the method raw material is easy to get, have that reactions steps is many, a defect such as complex operation, yield low (approximately 30%), part material toxicity are large.
As can be seen here,, still there is more deficiency in synthetic method the imperfection of existing end phenyl or substituted-phenyl long-chain fat mercaptan, is difficult to realize industrialization.Therefore, research and develop that a kind of reaction raw materials is cheaply easy to get, operational condition is gentle, yield and efficiency synthetic method high, that be easy to the end phenyl realizing economic environmental protection and have industrialized popularization value or substituted-phenyl long-chain fat mercaptan very necessary.
Summary of the invention
The synthetic method that the object of this invention is to provide a kind of end phenyl or substituted-phenyl long-chain fat mercaptan, to improve yield and the efficiency of target product, the condition that simplifies the operation, to the green industrialized production of realize target product.
End phenyl of the present invention or substituted-phenyl long-chain fat mercaptan synthetic method sulfhydrylation two step reaction of taking to treat different things alike after first Ge Shi coupling realize.
The first step, (replacement) phenyl-halide or (replacement) benzyl halide that general formula (1) or general formula (2) represent of take is reactant, the end halo long chain aliphatic alcohol representing with general formula (3) carries out form linked reaction, obtains end phenyl or substituted-phenyl long chain aliphatic alcohol that general formula (4) or general formula (5) represent.
Wherein, R is the substituting group on phenyl ring, is C
1-4alkyl or alkoxyl group, phenyl, benzyl; M represents substituent number on phenyl ring, is 0,1,2 or 3; N>=8; X represents halogen.
Preferably, described n is 9～20.
Second step, end phenyl or the substituted-phenyl long chain aliphatic alcohol that general formula (4) or general formula (5) represent of take is raw material, react with sulfhydrylization reagent thiocarbamide, obtain end phenyl or substituted-phenyl long-chain fat mercaptan that general formula (6) or general formula (7) represent.
Wherein, R is the substituting group on phenyl ring, is C
1-4alkyl or alkoxyl group, phenyl, benzyl; M represents substituent number on phenyl ring, is 0,1,2 or 3; N>=8.
Preferably, described n is 9～20.
The concrete reaction skeleton symbol of end phenyl of the present invention or substituted-phenyl long-chain fat mercaptan synthetic method is as follows.
In above-mentioned the first step reaction, under iodine in organic solvent causes, reactant (replacement) phenyl-halide or (replacement) benzyl halide first make corresponding Grignard reagent with MAGNESIUM METAL or metallic zinc reaction, wherein, the mol ratio of reactant and MAGNESIUM METAL or metallic zinc is 1 ︰ 1 ~ 10, preferably 1 ︰ 1.2 ~ 5; The mass volume ratio of reactant and organic solvent is 1 ︰ 1 ~ 15, preferably 1 ︰ 4 ~ 8.
(replacement) phenyl-halide or (replacement) benzyl halide of in the present invention, can be used as reactant include: chlorobenzene, bromobenzene, iodobenzene, Benzyl Chloride, cylite, iodate benzyl, PARA NITRO CHLOROBENZENE (PNCB), to methyl bromobenzene, to methoxyl group chlorobenzene, to methoxyl group bromobenzene, to methyl benzyl chloride, to methyl bromobenzyl, to methoxyl group benzyl chloride, to methoxyl group bromobenzyl, 4-ethyl chlorobenzene, 4-ethyl bromobenzene, 4-oxyethyl group chlorobenzene, 4-oxyethyl group bromobenzene, 4-ethyl benzyl chloride, 4-ethyl bromobenzyl, 4-oxyethyl group benzyl chloride, 4-oxyethyl group bromobenzyl, 4-IPC, 4-bromo-cumene, 4-sec.-propyl benzyl chloride, 4-sec.-propyl bromobenzyl, 3,5-dimethylated chlorobenzene, 3,5-dimethyl bromobenzene, 3,5-dimethoxy chlorobenzene, 3,5-dimethoxy bromobenzene, 3,5-dimethyl benzyl chloride, 3,5-dimethyl bromobenzyl, 3,5-dimethoxy-benzyl chloride, 3,5-dimethoxy bromobenzyl, 3,4,5-trimethylammonium chlorobenzene, 3,4,5-trimethylammonium bromobenzene, 3,4,5-trimethoxy chlorobenzene, 3,4,5-trimethoxy-bromobenzene, 3,4,5-trimethylammonium benzyl chloride, 3,4,5-trimethylammonium bromobenzyl, 3,4,5-trimethoxy benzyl chloride, 3,4,5-trimethoxy bromobenzyl, 4-chlordiphenyl, 4-bromo biphenyl, 4-chlorodiphenyl methane, 4-diphenylmethane bromine etc.
Described organic solvent is following any one solvent: positive propyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran or toluene, the preferred organic solvent of the present invention is tetrahydrofuran (THF), 2-methyltetrahydrofuran or toluene.
Secondly, the end halo long chain aliphatic alcohol that organic solvent with identical with preparing grignard reagent is dissolved adds in the Grignard reagent of above-mentioned preparation, under reflux temperature, react 2 ~ 10h, reclaim organic solvent, hydrolysis, acid adjustment, filtration make end phenyl or substituted-phenyl long chain aliphatic alcohol, wherein, the mol ratio of Grignard reagent and end halo long chain aliphatic alcohol is 2 ~ 3 ︰ 1, preferably 2.05 ~ 2.15 ︰ 1; The mass volume ratio of end halo long chain aliphatic alcohol and organic solvent is 1 ︰ 1 ~ 15, preferably 1 ︰ 4 ~ 8.
Carbon chain lengths >=8 of the end halo long chain aliphatic alcohol described in the present invention, generally get carbon chain lengths and be 9 ~ 20 end halo long chain aliphatic alcohol, as 9-chloro nonyl alcohol, 10-iodo decyl alcohol, 11-bromo undecyl alcohol, 12-chloro lauryl alcohol, 18-chloro stearyl alcohol, 20-bromo eicosanol, etc.
In the present invention, at-10 ~ 120 ℃, described end halo long chain aliphatic alcohol is added in Grignard reagent, preferred mixing temperature is 30 ~ 60 ℃.Hybrid mode is general selects end halo long chain aliphatic alcohol organic solvent drop to enter in Grignard reagent, time for adding 0.5 ~ 5h, preferably 1 ~ 1.5h.
Preferably, described reflux time is 4 ~ 6h.
The way of recycling of described organic solvent adopts the mode of concentrating under reduced pressure after first normal pressure.The amount of water of hydrolysis is suitable with the volume that reclaims organic solvent; PH value to 2 ~ 6 of regulation system when acid adjustment is processed, preferably pH value 2.5 ~ 3.5.Acid adjustment comprises various organic acids or mineral acid with reagent, as HAc, HCOOH, HCl, HBr, HI, H
2sO
4deng, preferred haloid acid.
The above-mentioned end phenyl preparing or substituted-phenyl long chain aliphatic alcohol can wash, dry after for next step mercaptolation, also drying not, directly carries out second step mercaptolation.
In above-mentioned second step reaction, under auxiliary reagent effect, end phenyl prepared by the first step or substituted-phenyl long chain aliphatic alcohol and the sulfhydrylization reagent thiocarbamide mercaptolation for the treatment of different things alike, under reflux temperature, react 2 ~ 10h, make target product end phenyl or substituted-phenyl long-chain fat mercaptan, wherein, the mol ratio of end phenyl or substituted-phenyl long chain aliphatic alcohol and sulfhydrylization reagent is 1 ︰ 1 ~ 10, preferably 1 ︰ 2 ~ 6.
Described auxiliary reagent is haloid acid, comprises HCl, HBr or HI, preferred HBr, and the mass concentration of described auxiliary reagent is greater than 40%, and preferably 48%.The mol ratio of end phenyl or substituted-phenyl long chain aliphatic alcohol and auxiliary reagent is 1 ︰ 1 ~ 20, preferably 1 ︰ 8 ~ 12.
Preferably, described reflux time is 4 ~ 6h.
The end phenyl preparing or substituted-phenyl long-chain fat mercaptan successively after adjusting alkali, acid adjustment, layering, refining, drying treatment, obtain final target product again.Wherein, described tune alkaline purification is pH value to 8 ~ 11 of regulation system, preferably 9.0 ~ 9.5, and adjust alkali reagent to comprise mineral alkali or organic bases, as NaOH, KOH, Na
2cO
3, K
2cO
3, NaHCO
3, KHCO
3, MeONa, EtONa, Et
3n etc., preferably NaOH, KOH or Na
2cO
3.After adjusting alkali, continue back flow reaction 1 ~ 8h, preferably 2h ~ 3h.It is pH value to 1 ~ 5 of regulation system that described acid adjustment is processed, preferably 2.5 ~ 3.0, and acid adjustment reagent comprises mineral acid or organic acid, as HCl, HBr, HI, H
2sO
4, HCOOH, HAc etc., preferably Hydrogen bromide.System stratification after acid adjustment is processed.Described refinement treatment be by isolated organic layer with solvent molten clear after, according to conventional process for refining decolour successively, dehydration, concentration, the preferred lower aliphatic alcohols of solvent used, as methyl alcohol, ethanol, Virahol etc.Target product end phenyl or substituted-phenyl long-chain fat mercaptan after concentrated are dried with vacuum suction drying mode.
End phenyl provided by the invention or substituted-phenyl long-chain fat mercaptan synthetic method, the yield of the first step Ge Shi linked reaction can reach more than 82%, and purity is more than 97%; The treat different things alike yield of mercaptolation of second step can reach more than 95%, and purity is more than 98.5%.
In synthetic method of the present invention, the intermediate product end phenyl of the first step Ge Shi linked reaction or substituted-phenyl long chain aliphatic alcohol can be directly used in the second step mercaptolation for the treatment of different things alike without drying treatment, wherein after acid adjustment, filtrate can be hydrolyzed workshop section for lower batch by time, finally by simple concentration, can take out by-product magnesium halide or zinc halide, when concentrated, condensation recycle-water can continue cover for being hydrolyzed workshop section; The second step mercaptolation tail gas alkali liquor absorption for the treatment of different things alike, minute water-yielding stratum can be taken out by-product sodium halide or potassium halide through a simple concentration; Finally realize the environmental protection of technique of the present invention.
The present invention proposes the sulfhydrylation for the treatment of different things alike after first Ge Shi coupling and prepare the synthetic method of end phenyl or substituted-phenyl long-chain fat mercaptan, overcome the deficiency of existing end phenyl or substituted-phenyl long-chain fat mercaptan synthetic method, compared with the conventional method, the plurality of advantages such as synthetic method of the present invention has mild condition, simple to operate, aftertreatment is easy, constant product quality, preparation efficiency are high, technique environmental protection, have industrial prospect and promotional value.
Embodiment
The preparation of embodiment 1:12-phenyl lauryl mercaptan
Get the new bromobenzene steaming of 15.7g, add the new tetrahydrofuran (THF) 80ml steaming of dehydration, mix rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add the new steaming of 10ml dehydration tetrahydrofuran (THF), 3.0g to activate 1 ~ 2 of magnesium chips, initiator iodine, oil bath temperature control, at 35 ~ 40 ℃, is placed in dropping funnel by the bromobenzene tetrahydrofuran (THF) diluent preparing.Logical N
2drive the air in system away, first the disposable bromobenzene diluent of approximately 1/10th volumes that adds is in reaction flask, and in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip bromobenzene diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new tetrahydrofuran (THF) that steams of a small amount of dehydration washs, filter cake cover is for the preparation of lower batch of Grignard reagent, filtrate and washings are weighed (about 90g) and detection level (approximately 25.8%) after merging, be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 45 ~ 50 ℃.The new tetrahydrofuran (THF) that steams of 14.0g12-bromo lauryl alcohol and 70ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, then 12-bromo lauryl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and lifts temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent tetrahydrofuran (THF) to not going out stream, be down to room temperature, add water 120ml, stir rear with Hydrogen bromide regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 12-phenyl lauryl alcohol 11.9g, yield 86.0%, purity 98.4%; FT-IR σ/cm
-1: 3375,2966,2850,1465,1346,1209,1058,1035,725,644,599;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.37-7.13 (m, 5H), 3.63 (t, 1H), 2.62 (t, 2H), 2.52 (m, 2H), 1.64 (q, 2H), 1.56 (q, 2H), 1.42-1.21 (m, 16H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-product magnesium bromide of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 12-phenyl lauryl alcohol 13.1g, 48% Hydrogen bromide 75.0g, thiocarbamide 13.5g is in 250ml reaction flask, lift temperature to backflow, clock reaction 4 ~ 5h, be cooled to 60 ~ 70 ℃, with 40% NaOH solution regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, standing 0.5 ~ 1h after stirring, divide water-yielding stratum to collect unified processing (can take out by-product Sodium Bromide through simply concentrated), organic layer adds after the dilution of 100ml methyl alcohol, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled dry, obtain target product 12-phenyl lauryl mercaptan 13.6g, yield 97.8%, purity 99.0%, FT-IR σ/cm
-1: 3608,2925,2850,1610,1500,1008,850,803,725,644,599,
1h-NMR(400MHz, CDCl
3) δ/ppm:7.33-7.25 (m, 5H), 2.64 (t, 2H), 2.55 (p, 2H), 1.63-1.58 (m, 5H), 1.51-1.28 (m, 16H).
The preparation of embodiment 2:12-p-methoxyphenyl lauryl mercaptan
Get 14.3g new steam to methoxyl group chlorobenzene, add the new 2-methyltetrahydrofuran 90ml steaming of dehydration, mix rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add 1 ~ 2 of the new 2-of steaming of 10ml dehydration methyltetrahydrofuran, 9.8g activated zinc powder, initiator iodine, oil bath temperature control, at 50 ~ 60 ℃, is placed in dropping funnel by what prepare to methoxyl group chlorobenzene 2-methyltetrahydrofuran diluent.Logical N
2drive the air in system away, first disposable add 1/10th volumes to methoxyl group chlorobenzene diluent in reaction flask, in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip methoxyl group chlorobenzene diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new 2-of steaming of a small amount of dehydration methyltetrahydrofuran washs, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 97g weighs, detection level approximately 21.0%), be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 60 ~ 70 ℃.The new 2-methyltetrahydrofuran that steams of 10.5g 12-chloro lauryl alcohol and 80ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, then 12-chloro lauryl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and lifts temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent 2-methyltetrahydrofuran to not going out stream, be down to room temperature, add water 150ml, stir rear with 1:1 hydrochloric acid regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 12-p-methoxyphenyl lauryl alcohol 12.2g, yield 87.8%, purity 98.1%; FT-IR σ/cm
-1: 3369,3349,2936,2922,2912,2873,2836,1612,1584,1513,1464,1442,1301,1247,1176,1039,823,811,720,563;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.11-6.82 (m, 4H), 3.73 (s, 3H), 3.51 (t, 1H), 2.75 (t, 2H), 1.66 (q, 2H), 1.58 (m, 2H), 1.56 (q, 2H), 1.42-1.21 (m, 16H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-produced zinc chloride of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 12-p-methoxyphenyl lauryl alcohol 14.6g, 48% Hydrogen bromide 80.0g, thiocarbamide 15.0g is in 250ml reaction flask, lift temperature to backflow, clock reaction 5 ~ 6h, be cooled to 60 ~ 70 ℃, with 30% KOH regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, standing 0.5 ~ 1h after stirring, divide water-yielding stratum to collect unified processing (can take out by-product Potassium Bromide through simply concentrated), organic layer adds after the dilution of 100ml methyl alcohol, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled dry, obtain target product 12-p-methoxyphenyl lauryl mercaptan 14.7g, yield 95.5%, purity 99.3%, FT-IR σ/cm
-1: 3475,2940,2865,1611,1510,1440,1242,1021,814,620,566,
1h-NMR(400MHz, CDCl
3) δ/ppm:7.24-7.13 (m, 4H), 2.61 (t, 2H), 2.53 (p, 2H), 1.61-1.54 (m, 5H), 1.52-1.26 (m, 16H).
The preparation of embodiment 3:10-(3`, 5`-xylyl)-decyl mercaptan
Get 3 of the new steaming of 11.6g, 5-dimethyl iodobenzene, adds the new tetrahydrofuran (THF) 80ml steaming of dehydration, mixes rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add the new steaming of 10ml dehydration tetrahydrofuran (THF), 2.1g to activate 1 ~ 2 of magnesium chips, initiator iodine, oil bath temperature control is at 35 ~ 40 ℃, by prepare 3,5-dimethyl iodobenzene tetrahydrofuran (THF) diluent is placed in dropping funnel.Logical N
2drive the air in system away, first disposable 3 of 1/10th volumes that add, 5-dimethyl iodobenzene diluent is in reaction flask, in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continues to drip 3,5-dimethyl iodobenzene diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new tetrahydrofuran (THF) that steams of a small amount of dehydration washs, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 84g weighs, detection level approximately 14.8%), be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 45 ~ 50 ℃.The new tetrahydrofuran (THF) that steams of 6.6g 10-iodo decyl alcohol and 50ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, then 10-iodo decyl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and continues to lift temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent tetrahydrofuran (THF) to not going out stream, be down to room temperature, add water 110ml, stir rear with hydroiodic acid HI regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 10-(3`, 5`-xylyl)-decyl alcohol 5.1g, yield 83.7%, purity 97.9%; FT-IR σ/cm
-1: 3324,3014,2919,2868,1609,1453,1379,1361,1299,1157,1055,1040,990,848,714,690,645,514;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.09-6.92 (s, 3H), 4.55 (m, 2H), 3.62 (t, 1H), 2.73 (t, 2H), 2.30 (s, 6H), 1.63 (m, 2H), 1.58 (q, 2H), 1.51-1.23 (m, 12H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-product magnesium iodide of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 10-(3`, 5`-xylyl)-decyl alcohol 13.1g, 48% Hydrogen bromide 75.0g, thiocarbamide 13.5g is in 250ml reaction flask, lift temperature to backflow, clock reaction 5 ~ 6h, be cooled to 60 ~ 70 ℃, with 30% KOH regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, standing 0.5 ~ 1h after stirring, divide water-yielding stratum to collect unified processing (can take out by-product Potassium Bromide through simply concentrated), organic layer adds after 100ml alcohol dilution, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled dry, obtain target product 10-(3`, 5`-xylyl)-decyl mercaptan 13.4g, yield 96.4%, purity 98.9%, FT-IR σ/cm
-1: 3348,3022,2920,2852,1615,1462,1380,1284,1152,1048,989,831,701,638,528,
1h-NMR(400MHz, CDCl
3) δ/ppm:7.13-6.99 (s, 3H), 4.57 (m, 2H), 2.72 (t, 2H), 2.35 (s, 6H), 1.65-1.57 (m, 5H), 1.47-1.20 (m, 12H).
The preparation of embodiment 4:12-phenyl lauryl mercaptan
Get the new benzyl chloride steaming of 12.7g, add the new tetrahydrofuran (THF) 90ml steaming of dehydration, mix rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add new 1 ~ 2 of the tetrahydrofuran (THF), 11.0g activating powder, initiator iodine that steams of 10ml dehydration, oil bath temperature control, at 35 ~ 40 ℃, is placed in dropping funnel by the benzyl chloride diluent preparing.Logical N
2drive the air in system away, first the disposable benzyl chloride tetrahydrofuran (THF) diluent of 1/10th volumes that adds is in reaction flask, and in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip benzyl chloride diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new tetrahydrofuran (THF) that steams of a small amount of dehydration washs, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 98g weighs, detection level approximately 15.1%), be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 45 ~ 50 ℃.The new tetrahydrofuran (THF) that steams of 9.0g 11-chloro undecyl alcohol and 70ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, then 11-chloro undecyl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and continues to lift temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent tetrahydrofuran (THF) to not going out stream, be down to room temperature, add water 150ml, after stirring, with 1:1 hydrochloric acid regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, obtain intermediate product 12-phenyl lauryl alcohol wet product 14.8g, without the dry second step that is directly used in, react.Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-product of magnesium chloride of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get step intermediate product 12-phenyl lauryl alcohol wet product 14.8g, 48% Hydrogen bromide 70g, thiocarbamide 12.5g in 250ml reaction flask, lift temperature to backflow, clock reaction 4 ~ 5h, is cooled to 60 ~ 70 ℃, uses Na
2cO
3regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, standing 0.5 ~ 1h after stirring, divide water-yielding stratum to collect unified processing (can take out by-product Sodium Bromide through simply concentrated), organic layer adds after the dilution of 100ml methyl alcohol, via activated carbon decolorizing, anhydrous magnesium sulfate, dewatering, concentrate, reduce pressure successively, it is dry to bleed, obtain target product 12-phenyl lauryl mercaptan 10.5g, yield 80.2%(is in 11-chloro undecyl alcohol), purity 98.7%; FT-IR σ/cm
-1: 3603,2921,2848,1609,1500,1002,850,803,724,645,599;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.32-7.25 (m, 5H), 2.65 (t, 2H), 2.54 (p, 2H), 1.63-1.57 (m, 5H), 1.53-1.28 (m, 16H).
The preparation of embodiment 5:11-(3`, 4`, 5`-2,4,5-trimethoxyphenyl)-undecyl mercaptan
Get 3,4 of 12.4g dehydration refinement treatment, 5-trimethoxy-bromobenzene, adds the new tetrahydrofuran (THF) 95ml steaming of dehydration, mixes rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add the new steaming of 10ml dehydration tetrahydrofuran (THF), 3.6g to activate 1 ~ 2 of magnesium chips, initiator iodine, oil bath temperature control is at 35 ~ 40 ℃, by prepare 3,4,5-trimethoxy-bromobenzene diluent is placed in dropping funnel.Logical N
2drive the air in system away, first disposable 3 of 1/10th volumes that add, 4,5-trimethoxy-bromobenzene diluent is in reaction flask, and in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip 3,4,5-trimethoxy-bromobenzene diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new tetrahydrofuran (THF) that steams of a small amount of dehydration washs, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 101g weighs, detection level approximately 13.4%), be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 45 ~ 50 ℃.The new tetrahydrofuran (THF) that steams of 6.0g 11-bromo undecyl alcohol and 45ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, 11-bromo undecyl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and continues to lift temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent tetrahydrofuran (THF) to not going out stream, be down to room temperature, add water 130ml, stir rear with Hydrogen bromide regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 11-(3`, 4`, 5`-2,4,5-trimethoxyphenyl)-undecyl alcohol 6.7g, yield 82.9%, purity 98.0%; FT-IR σ/cm
-1: 3428,2998,2941,2881,2839,1593,1508,1461,1422,1361,1331,1237,1128,1062,1006,961,829,780,688,582;
1h-NMR(400MHz, CDCl
3) δ/ppm:6.55 (s, 2H), 4.55 (s, 2H), 3.80 (s, 9H), 3.62 (t, 1H), 2.73 (t, 2H), 1.68 (q, 2H), 1.58 (m, 2H), 1.51-1.23 (m, 14H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-product magnesium bromide of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 11-(3`, 4`, 5`-2,4,5-trimethoxyphenyl)-undecyl alcohol 16.9g, 48% Hydrogen bromide 85g, thiocarbamide 16.5g is in 250ml reaction flask, lift temperature to backflow, clock reaction 5 ~ 6h, be cooled to 60 ~ 70 ℃, with 40% NaOH regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, stir even rear standing 0.5 ~ 1h, divide water-yielding stratum to collect unified processing (can take out by-product Sodium Bromide through simply concentrated), organic layer adds after the dilution of 100ml methyl alcohol, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled and is drying to obtain target product 11-(3`, 4`, 5`-2,4,5-trimethoxyphenyl)-undecyl mercaptan 16.9g, yield 95.5%, purity 98.6%, FT-IR σ/cm
-1: 3445,3012,3001,2892,2840,1611,1510,1466,1422,1357,1321,1232,1133,1058,997,954,830,753,680,573,531,
1h-NMR(400MHz, CDCl
3) δ/ppm:6.54 (s, 2H), 4.56 (s, 2H), 3.78 (s, 9H), 2.71 (t, 2H), 1.63-1.54 (m, 5H), 1.43-1.20 (m, 14H).
The preparation of embodiment 6:18-p-methylphenyl stearylmercaptan
Get the new parachlorotoluene steaming of 12.7g, add the new 2-methyltetrahydrofuran 100ml steaming of dehydration, mix rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add 1 ~ 2 of the new 2-of steaming of 10ml dehydration methyltetrahydrofuran, 13.0g activated zinc powder, initiator iodine, oil bath temperature control, at 50 ~ 60 ℃, is placed in dropping funnel by the parachlorotoluene diluent preparing.Logical N
2drive the air in system away, first the disposable parachlorotoluene diluent of 1/10th volumes that adds is in reaction flask, and in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip parachlorotoluene diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new 2-methyltetrahydrofuran washing of steaming of a small amount of dehydration, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 110g weighs, detection level approximately 17.1%), be placed in the dry four-hole bottle of another 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 60 ~ 70 ℃.14.4g 18-chloro stearyl alcohol is mixed and is placed in dropping funnel with the new 2-methyltetrahydrofuran steaming of 70ml dehydration.Logical N
2drive the air in system away, 18-chloro stearyl alcohol diluent is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and continues to lift temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent 2-methyltetrahydrofuran to not going out stream, be down to room temperature, add water 150ml, stir rear with 1:1 hydrochloric acid regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 18-p-methylphenyl stearyl alcohol 14.0g, yield 82.3%, purity 97.9%; FT-IR σ/cm
-1: 3345,3092,3049,3023,3005,2940,2926,2871,2732,1516,1449,1442,1436,1379,1275,1216,1167,1111,1048,849,808,758,720,653,557,547;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.09-7.05 (m, 4H), 3.72 (m, 2H), 3.52 (t, 1H), 2.79 (t, 2H), 2.29 (s, 3H), 1.71 (q, 2H), 1.62 (m, 2H), 1.45-1.23 (m, 28H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-produced zinc chloride of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 18-p-methylphenyl stearyl alcohol 18.0g, 48% Hydrogen bromide 80.0g, thiocarbamide 15.0g is in 250ml reaction flask, lift temperature to backflow, clock reaction 4 ~ 5h, be cooled to 60 ~ 70 ℃, with 35% KOH regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, stir even rear standing 0.5 ~ 1h, divide water-yielding stratum to collect unified processing (can take out by-product Potassium Bromide through simply concentrated), organic layer adds after 100ml isopropanol, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled and is drying to obtain target product 18-p-methylphenyl stearylmercaptan 18.3g, yield 97.3%, purity 99.1%, FT-IR σ/cm
-1: 3387,3100,3040,2983,2936,2852,2720,1521,1452,1440,1382,1264,1121,1050,852,800,755,710,653,551,
1h-NMR(400MHz, CDCl
3) δ/ppm:7.08-7.03 (m, 4H), 3.73 (m, 2H), 2.78 (t, 2H), 2.29 (s, 3H), 1.73-1.64 (m, 5H), 1.51-1.25 (m, 28H).
The preparation of embodiment 7:20-to xenyl 20 mercaptan
Get 23.3g new steam to bromo biphenyl, add the new toluene 120ml steaming of dehydration, mix rear airtight stand-by.In the dry four-hole bottle of the 250ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, add the new steaming of 20ml dehydration toluene, 12.0g to activate 2 ~ 3 of magnesium chips, initiator iodine, oil bath temperature control, at 70 ~ 80 ℃, is placed in dropping funnel by what prepare to bromo biphenyl diluent.Logical N
2drive the air in system away, first disposable add 1/10th volumes to bromo biphenyl diluent in reaction flask, in question response bottle, liquid starts micro-boil and after the color of iodine fades away, maintenance system temperature, continue to drip bromo biphenyl diluent, approximately 1 ~ 1.5h adds, then insulation reaction 2 ~ 3h.Fast filtering, the new toluene wash of steaming of a small amount of dehydration, filter cake cover is for the preparation of lower batch of Grignard reagent, after filtrate and washings merge, (about 127g weighs, detection level approximately 19.8%), be placed in the dry four-hole bottle of another 500ml that is furnished with prolong (upper end dress drying tube), mechanical stirring, thermometer, dropping funnel, oil bath temperature control is at 80 ~ 90 ℃.The new toluene that steams of 17.8g 20-bromo eicosanol and 100ml dehydration is mixed and is placed in dropping funnel.Logical N
2drive the air in system away, the diluent of 20-bromo eicosanol is slowly splashed in reaction flask, approximately 1 ~ 1.5h drips off, and continues to lift temperature to backflow, clock reaction 4 ~ 5h.Change back receiving apparatus, adopt concentrating under reduced pressure mode after first normal pressure, reclaim solvent toluene to not going out stream, be down to room temperature, add water 200ml, stir rear with Hydrogen bromide regulation system pH value to 3 ~ 3.5, continue to stir 30min, after repetition measurement pH value is constant, be cooled to 10 ~ 15 ℃, filter, washing, dry, obtain off-white color intermediate product 20-to xenyl eicosanol 17.6g, yield 82.8%, purity 97.1%; FT-IR σ/cm
-1: 3343,3241,3034,2924,2874,1490,1451,1407,1369,1124,1084,1040,1018,1005,1000,986,851,820,762,752,733,704,689,510;
1h-NMR(400MHz, CDCl
3) δ/ppm:7.58-7.34 (m, 9H), 4.68 (m, 2H), 3.64 (t, 1H), 2.75 (t, 2H), 1.65 (m, 2H), 1.54 (q, 2H), 1.43-1.22 (m, 32H).Filtrate and washings merge cover for lower batch of hydrolysis workshop section, time with after the simple concentrated by-product magnesium bromide of taking out again, condensation recycle-water continues to overlap and is used for being hydrolyzed workshop section.
Get intermediate product 20-to xenyl eicosanol 22.5g, 48% Hydrogen bromide 85g, thiocarbamide 16.5g is in 250ml reaction flask, lift temperature to backflow, clock reaction 5 ~ 6h, be cooled to 60 ~ 70 ℃, with 40% NaOH regulation system pH value to 9.0 ~ 9.5, continue temperature raising back flow reaction 2 ~ 3h, again be cooled to 40 ~ 50 ℃, with Hydrogen bromide regulation system pH value to 2.5 ~ 3.0, stir even rear standing 0.5 ~ 1h, divide water-yielding stratum to collect unified processing (can take out by-product Sodium Bromide through simply concentrated), organic layer adds after 100ml alcohol dilution, successively via activated carbon decolorizing, anhydrous magnesium sulfate dehydration, concentrated, decompression is bled and is drying to obtain target product 20-to xenyl 20 mercaptan 22.2g, yield 95.3%, purity 98.5%, FT-IR σ/cm
-1: 3348,3238,3030,2926,2866,1486,1450,1400,1370,1131,1100,1028,1001,986,846,811,760,747,730,702,683,514,
1h-NMR(400MHz, CDCl
3) δ/ppm:7.56-7.31 (m, 9H), 4.66 (m, 2H), 2.72 (t, 2H), 1.66-1.52 (q, 5H), 1.52-1.23 (m, 32H).
Claims (9)
1. end phenyl or substituted-phenyl long-chain fat mercaptan synthetic method, take first Ge Shi coupling, after sulfhydrylation two step reaction for the treatment of different things alike realize, it is characterized in that:
The first step, (replacement) phenyl-halide or (replacement) benzyl halide that general formula (1) or general formula (2) represent of take is reactant, the end halo long chain aliphatic alcohol representing with general formula (3) carries out form linked reaction, obtains end phenyl or substituted-phenyl long chain aliphatic alcohol that general formula (4) or general formula (5) represent;
Wherein, R is the substituting group on phenyl ring, is C
1-4alkyl or alkoxyl group, phenyl, benzyl; M represents substituent number on phenyl ring, is 0,1,2 or 3; N>=8; X represents halogen;
Second step, end phenyl or the substituted-phenyl long chain aliphatic alcohol that general formula (4) or general formula (5) represent of take is raw material, react with sulfhydrylization reagent thiocarbamide, obtain end phenyl or substituted-phenyl long-chain fat mercaptan that general formula (6) or general formula (7) represent;
Wherein, R is the substituting group on phenyl ring, is C
1-4alkyl or alkoxyl group, phenyl, benzyl; M represents substituent number on phenyl ring, is 0,1,2 or 3; N>=8.
2. end phenyl according to claim 1 or substituted-phenyl long-chain fat mercaptan synthetic method, is characterized in that described n is 9～20.
3. end phenyl according to claim 1 or substituted-phenyl long-chain fat mercaptan synthetic method, it is characterized in that described the first step reaction is under the iodine initiation in organic solvent, reactant (replacement) phenyl-halide or (replacement) benzyl halide make corresponding Grignard reagent with MAGNESIUM METAL or metallic zinc reaction, the end halo long chain aliphatic alcohol that organic solvent with identical with preparing grignard reagent is dissolved adds in the Grignard reagent of above-mentioned preparation, under reflux temperature, react 2 ~ 10h, reclaim organic solvent, hydrolysis, acid adjustment, filtration makes end phenyl or substituted-phenyl long chain aliphatic alcohol, wherein, the mol ratio of reactant and MAGNESIUM METAL or metallic zinc is 1 ︰ 1 ~ 10, the mass volume ratio of reactant and organic solvent is 1 ︰ 1 ~ 15, the mol ratio of Grignard reagent and end halo long chain aliphatic alcohol is 2 ~ 3 ︰ 1, the mass volume ratio of end halo long chain aliphatic alcohol and organic solvent is 1 ︰ 1 ~ 15.
4. end phenyl according to claim 3 or substituted-phenyl long-chain fat mercaptan synthetic method, the mol ratio that it is characterized in that reactant and MAGNESIUM METAL or metallic zinc is 1 ︰ 1.2 ~ 5, the mass volume ratio of reactant and organic solvent is 1 ︰ 4 ~ 8, the mol ratio of Grignard reagent and end halo long chain aliphatic alcohol is 2.05 ~ 2.15 ︰ 1, and the mass volume ratio of end halo long chain aliphatic alcohol and organic solvent is 1 ︰ 4 ~ 8.
5. end phenyl according to claim 3 or substituted-phenyl long-chain fat mercaptan synthetic method, is characterized in that described organic solvent is for following any one solvent: positive propyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran or toluene.
6. end phenyl according to claim 5 or substituted-phenyl long-chain fat mercaptan synthetic method, is characterized in that described organic solvent is tetrahydrofuran (THF), 2-methyltetrahydrofuran or toluene.
7. end phenyl according to claim 1 or substituted-phenyl long-chain fat mercaptan synthetic method, it is characterized in that described second step reaction is under the effect of auxiliary reagent haloid acid, end phenyl prepared by the first step or substituted-phenyl long chain aliphatic alcohol react 2 ~ 10h with sulfhydrylization reagent thiocarbamide under reflux temperature, make target product end phenyl or substituted-phenyl long-chain fat mercaptan, wherein, the mol ratio of end phenyl or substituted-phenyl long chain aliphatic alcohol and sulfhydrylization reagent is 1 ︰ 1 ~ 10, the mol ratio of end phenyl or substituted-phenyl long chain aliphatic alcohol and auxiliary reagent is 1 ︰ 1 ~ 20.
8. end phenyl according to claim 7 or substituted-phenyl long-chain fat mercaptan synthetic method, the mol ratio that it is characterized in that described end phenyl or substituted-phenyl long chain aliphatic alcohol and sulfhydrylization reagent is 1 ︰ 2 ~ 6, and the mol ratio of end phenyl or substituted-phenyl long chain aliphatic alcohol and auxiliary reagent is 1 ︰ 8 ~ 12.
9. end phenyl according to claim 7 or substituted-phenyl long-chain fat mercaptan synthetic method, is characterized in that described auxiliary reagent is HBr.
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|---|---|---|---|---|
| JPH01268673A (en) * | 1988-04-20 | 1989-10-26 | Nisso Yuka Kogyo Kk | Production of mercaptan compound |
| CN1503772A (en) * | 2001-04-23 | 2004-06-09 | 石原产业株式会社 | Process for the preparation of benzyl alcohols |
| CN103058823A (en) * | 2012-12-26 | 2013-04-24 | 淮安万邦香料工业有限公司 | Preparation method of 2-dimethyl-2-octanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01268673A (en) * | 1988-04-20 | 1989-10-26 | Nisso Yuka Kogyo Kk | Production of mercaptan compound |
| CN1503772A (en) * | 2001-04-23 | 2004-06-09 | 石原产业株式会社 | Process for the preparation of benzyl alcohols |
| CN103058823A (en) * | 2012-12-26 | 2013-04-24 | 淮安万邦香料工业有限公司 | Preparation method of 2-dimethyl-2-octanol |
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|---|---|---|---|---|
| CN115010632A (en) * | 2022-07-07 | 2022-09-06 | 浙江大学衢州研究院 | Green synthesis method of thiol compounds |
| CN115010632B (en) * | 2022-07-07 | 2023-09-01 | 浙江大学衢州研究院 | Green synthesis method of mercaptan compounds |
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