CN1469861A - 用于制备苯硫酚的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 phenoxy, phenylthio Chemical group 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 45
- 239000005864 Sulphur Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 6
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- 150000001989 diazonium salts Chemical class 0.000 description 5
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- 239000002253 acid Substances 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 2
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- 125000002541 furyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JAFTYCKQJPKEEX-UHFFFAOYSA-N 2-amino-6-(1-hydroxyethyl)benzoic acid Chemical compound CC(O)C1=CC=CC(N)=C1C(O)=O JAFTYCKQJPKEEX-UHFFFAOYSA-N 0.000 description 1
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 1
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
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- 238000006193 diazotization reaction Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000004305 thiazinyl group Chemical group S1NC(=CC=C1)* 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/26—Thiols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
Abstract
一种制备式I苯硫酚的方法：式I中n是1－5的整数，以及R是氢、烷基、羟烷基、烷氨基、二烷基氨基、链烯基、链炔基、烷氧基、烷硫基、苯基、萘基、苯氧基、苯硫基、羟基、巯基、羧基、磺酸基、或杂环基，通过式II的苯基重氮盐与硫在升高的温度下在含水碱的存在下反应然后分离式I化合物，式II中n和R定义如上，X是卤素或硫酸氢根。
Description
本发明涉及一种制备苯硫酚的新方法以及它们作为中间体在制备异苯并呋喃酮类型的除草剂中的用途。
根据Methoden der organischen Chemie(Houben-Weyl)，Volume 9，12(1955)，通过例如苯胺重氮化然后将得到的重氮盐与乙基黄原酸钾在碱性醇介质中反应可得到苯硫酚。Chem.Ber.10，2959(1968)公开了将苯基重氮盐与多硫化钠反应可得到苯硫酚。根据The Chemistry of the Thiol Group，part 1，220(1974)和Chem.Ber.120，1161，还可使用二硫化物代替多硫化物，在Pestic.Sci.1996，47，332中描述了硫化钠可作为适合的试剂。
现已惊奇地发现，如果在相应的苯基重氮盐反应中，使用单质硫代替黄原酸盐、多硫化物或硫化物，可以明显改进苯硫酚的制备。
因此，本发明涉及一种制备下式苯硫酚的方法：其中n是1-5的整数，且R是氢、烷基、羟烷基、烷氨基、二烷基氨基、链烯基、链炔基、烷氧基、烷硫基、苯基、萘基、苯氧基、苯硫基、羟基、巯基、羧基、磺酸基、羟氨基或杂环基，通过下式的苯基重氮盐与硫在升高的温度下在含水碱的存在下反应然后分离式I化合物，其中n和R定义如上，X是卤素或硫酸氢根。
在式I化合物中，n优选是1-3的整数。n特别是2。已经发现那些具有羧基或磺酸基或其盐的式I化合物特别适合并且特别有价值。尤其是，具有邻位羧基以及间位(3-位)羟烷基、特别是CH3CH(OH)基的式I化合物被证明是特别有益的。相应于该化合物的式II苯基重氮盐存在于水溶液中，在该水溶液中存在其与相应的闭合内酯7-巯基-3-甲基-3H-异苯并呋喃-1-酮的依赖于pH的水解平衡。该化合物可有利地用于制备异苯并呋喃酮类除草剂。
通常，式I和II化合物具有彼此相邻的能够形成(稠合)环的取代基，例如邻位羧基和间位羟烷基，这些化合物在水溶液中与相应的闭合形式——例如，内酯，特别是5-元环内酯形式，例如在酸溶液中非常容易形成的7-巯基-3-甲基-3H-异苯并呋喃-1-酮-—存在依赖于pH的平衡。通常，当环的尺寸变大时，成环的趋势减小，通常6-和7-元环比5-元环难于形成。
根据本发明的方法因此还包括制备其中两个取代基R形成稠合环的闭合形式的式I化合物。
在R定义中出现的烷基优选含有1-4个碳原子，例如甲基、乙基、丙基和丁基以及它们支化的异构体。优选的烷氧基、烷硫基和羟烷基衍生自上述烷基。链烯基和链炔基R优选具有2-4个碳原子，例如是乙烯基、丙烯基、乙炔基、丙炔基和丙烯基和它们支化的异构体、丁烯基和丁炔基和它们支化的和二不饱和的异构体。术语羟基(-OH)、巯基(-SH)和磺酸基(-SO3H)和羧基(-CO2H)还包括了每种基团的盐的形式，例如碱金属盐、碱土金属盐和胺盐。认为杂环基优选是4-元至8-元、饱和或不饱和的环，其含有至少一个选自氮、硫和氧的杂原子。它们的例子是吡啶基、呋喃基、噻吩基、氧杂环丁烷基、噻嗪基、吗啉基、哌嗪基、哒嗪基、吡嗪基、噻喃基、吡唑基、嘧啶基、三嗪基、异呋喃基、吡喃基、哌啶基、甲基吡啶基、噻二唑啉基、硫丁环基、***基、oxazolanyl、四氢噻吩基、丫庚因基、噻唑基、异噻唑基、咪唑基或吡咯基。
优选以粉末的形式使用硫。每摩尔苯基重氮盐优选使用1.2-5摩尔、特别是1.5-3摩尔硫。
用公知方法，在约-5℃-+5℃将亚硝酸钠溶液计量加入到相应的胺在水中的酸溶液中制备重氮盐。
术语“升高的温度”优选表示20-100℃的温度范围。特别有利的是在30-80℃进行。
适合的含水碱优选是碱金属氢氧化物或碱土金属氢氧化物或氨的水溶液。优选每摩尔重氮盐使用2.5-5摩尔、特别是1.5-3摩尔的碱。如果式II的苯基重氮盐已经含有酸基作为取代基，优选另加入每个酸基所需量的碱。
根据本发明的方法具有很大的优点，其可以大规模工业化进行。工艺过程通常是将硫引入温度升高的含水碱中，然后计量加入式II的重氮盐。
根据本发明的方法可连续进行或间歇进行(不连续进行，分批进行)，优选间歇操作。间歇和连续反应过程均优选在搅拌釜或搅拌釜级联中进行。
已经发现，对于硫酚的分离，有利的是通过加入亚硫酸钠，亚硫酸氢钠或二氧化硫将过量的硫转化为硫代硫酸钠。然后酸化反应溶液，借此分离出硫酚并可与含水盐溶液分离。对于苯硫酚的进一步提纯，可以是蒸馏。
分离的硫酚的产率通常为80-100％。在反应混合物中化合物的产率通常为大于95％。
根据本发明的方法具有下述优于在先技术的优点：
—可以大规模工业化实施，
—反应过程简单，特别是与使用二硫化物的方法相比，在后者中，二硫化物的溶液和重氮溶液必须同时计量加入到含水碱中以防止重氮基与氢的交换，
—不生成毒性副产物，特别是在使用黄原酸盐的方法中在处理期间所形成的摩尔量的COS，
—与使用二硫化物和多硫化物的方法相比，反应的选择性非常高，
—得到高达98％的产物产率，
—可在多用途装置中进行。
根据本发明制备的式I硫酚可特别作为中间体用于异苯并呋喃酮类型的除草剂的制备，这在例如US-A-5332717和US-A-5428002中有所描述。
下面的实施例用于具体说明本发明。实施例1：7-巯基-3-甲基-3H-异苯并呋喃-1-酮的制备
在第一反应器中，将50％水溶液的形式(1.0mol)的203g 2-氨基-6-(1-羟基乙基)-苯甲酸(钠盐)和181g 40％亚硝酸钠水溶液(1.05mol)同时加入到428g盐酸中(32％)。反应完成后，过量的亚硝酸盐通过加入氨基磺酸破坏。
在第二反应器中，将800g 30％溶液形式的氢氧化钠和71g硫粉(2.20mol)加热到60℃，搅拌60分钟。将在第一反应器中制备的重氮盐溶液加入得到的混合物中，放出氮气，形成相应的硫酚。
为了处理，将300g甲苯和195g 40％水溶液形式的亚硫酸氢钠(0.75mol)加入反应混合物。在80℃，用乙酸将pH调节到8，结果，邻羟基苯甲酸内酯环闭合，过量的硫转化为硫代硫酸盐。在30℃，pH进一步降低到6，释放出硫酚，进入到甲苯相。分离甲苯相，加入5g三苯基膦和150g水。加热至约30℃，将pH调节到11，结果，钠盐形式的苯硫酚进入水相，由此可分离出钠盐形式的7-巯基-3-甲基-3H-异苯并呋喃-1-酮，以水溶液形式的产率为85％(基于2-氨基-6-(1-羟基乙基)苯甲酸)。
Claims (2)
1.一种制备下式苯硫酚的方法：
其中
n是1-5的整数，以及
R是氢、烷基、羟烷基、烷氨基、二烷基氨基、链烯基、链炔基、烷氧基、烷硫基、苯基、萘基、苯氧基、苯硫基、羟基、巯基、羧基、磺酸基或杂环基，
通过下式的苯基重氮盐与硫在升高的温度下在含水碱的存在下反应然后分离式I化合物，
其中n和R定义如上，X是卤素或硫酸氢根。
2.式I化合物在制备异苯并呋喃酮类型的除草剂中的用途。
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| CA2423300A1 (en) | 2002-04-18 |
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| KR100837098B1 (ko) | 2008-06-13 |
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| HU228460B1 (en) | 2013-03-28 |
| JP4021760B2 (ja) | 2007-12-12 |
| ATE380790T1 (de) | 2007-12-15 |
| EP1330434B1 (en) | 2007-12-12 |
| BR0114247A (pt) | 2004-02-10 |
| IL154804A0 (en) | 2003-10-31 |
| AU2002221663B2 (en) | 2004-09-30 |
| PL205784B1 (pl) | 2010-05-31 |
| HUP0301353A2 (hu) | 2003-09-29 |
| MXPA03003068A (es) | 2003-07-14 |
| BR0114247B1 (pt) | 2013-02-05 |
| US20040030135A1 (en) | 2004-02-12 |
| IL154804A (en) | 2011-01-31 |
| PL360543A1 (en) | 2004-09-06 |
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