TWI304804B - Process for the preparation of thiophenols - Google Patents
Process for the preparation of thiophenols Download PDFInfo
- Publication number
- TWI304804B TWI304804B TW090124907A TW90124907A TWI304804B TW I304804 B TWI304804 B TW I304804B TW 090124907 A TW090124907 A TW 090124907A TW 90124907 A TW90124907 A TW 90124907A TW I304804 B TWI304804 B TW I304804B
- Authority
- TW
- Taiwan
- Prior art keywords
- formula
- compound
- moles
- group
- sulfur
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- -1 phenoxy, phenylthio Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical group OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 150000001989 diazonium salts Chemical class 0.000 description 5
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002596 lactones Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 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
- 239000012991 xanthate Substances 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- FSXWCUSOFGPQKK-UHFFFAOYSA-N ethanebis(thioic s-acid) Chemical compound SC(=O)C(S)=O FSXWCUSOFGPQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 125000005305 thiadiazolinyl group Chemical group 0.000 description 1
- 125000002053 thietanyl group Chemical group 0.000 description 1
- 125000001166 thiolanyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- 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)
Description
1304804 · a7 __________B7____ 五、發明說明（） 本發明是關於一種新穎的製備苯硫酚之方法，及其作 爲製備異苯并呋喃酮型除草劑中間物之用途。 根據 Methoden der organischen Chemie (Houben-Weyl) 卷9，12 ( 1955)，苯硫酚能藉由，例如，重氮化苯胺，再 將所得重氮鹽與乙基黃原酸鉀在鹼性醇介質中反應而得 到。Chem. Ber. 10, 2959 ( 1968)揭示苯硫酚可經由將苯基 重氮鹽與多硫化鈉反應而得到。根據硫醇基化學第1部， 220 ( 1974)及Chem Ber. 120，1161，亦可用二硫化物代替 多硫化物，又硫化二鈉在Pestic. Sci. 1996, 47, 332中被描 述作爲合適的試劑。 現已驚訝的發現，如果在相對應的苯基重氮鹽類反應 中，用元素硫代替黃原酸鹽類、多硫化物或硫化物，能顯 著的改良苯硫酚的製備。 因此本發明是關於一種製備式I之苯硫酚的方法 (請先閱讀背面之沒意事項再填寫本頁)
SH
其中 η爲1至5的整數，及 、 R爲氫，烷基，羥烷基，烷胺基，二烷胺基，烯基， 快基’院氧基’院硫基，苯基，奈基’本串<基’本硫基’ 鹵素，羥基，氫硫基，羧基，磺酸基，羥胺基或雜環基， 係藉由將式II之苯基重氮鹽 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7
1304804 _____ B7 五、發明說明（） X' II， 其中η和R係如所定義的，及X爲鹵素或硫酸氫鹽， 在水性鹼存在下，在提高的溫度下與硫反應，再分離式I 化合物。 式I化合物中，η較佳爲1至3的整數。特別是η爲 2。已發現那些具有羧基或磺酸基的式I化合物或其鹽是特 別適合的及特別有用的。尤其是在鄰位具有羧基及在間位 (位置3)具有羥烷基，特別是C.H3CH(OH)基，的式I化 合物已被證明是特別有利的。對應於該化合物的式II之苯 基重氮鹽在水溶液中與對應的閉合內酯形式，7-氫硫基-3-甲基-3H-異苯并呋喃-1-酮，呈pH-依賴性水解平衡。該化 合物可有利的用於製備異苯并呋喃酮型除草劑。 一般而言，具有能一起形成（稠合）環之互相鄰接的 取代基（例如在鄰位的羧基與在間位的羥烷基）的式I及 II化合物，在水溶液中係與對應的閉合形式，例如內酯形 式，特別是5員環內酯形式，如7-氫硫基甲基-3H-異苯 并呋喃-1-酮（尤其在酸溶液中會立刻形成），呈pH_依賴 性平衡。通常，隨著環的大小的增加，環的形成趨向減 少。六及七員環一般較五員環不易形成。 因此，根據本發明的方法也包含製備那些其中的兩個 取代基R已形成稠合環的閉合形式的式I化合物。 5 ^— _ 本余氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----II — — —— — — · I I I (請先閱讀背面之注意事項再填寫本頁) 訂--------- 1304804 A7 _ B7 五、發明說明（） 出現在R定義中的院基較佳含有1至4個碳原子，及 例如是甲基，乙基，丙基及丁基及其支鏈異構物。較佳的 烷氧基，烷硫基及羥烷基係衍生自提到的院基。嫌基及炔 基R較佳具有2至4個碳原子，及例如是乙稀基，丙烯 - 基，乙炔基’丙炔基及丙烯基和其支鏈異構物，以及丁烯 基和丁炔基及其支鏈和二-不飽和異構物。經基（_〇H), 氫硫基（-SH)及磺酸基（-SCXH)及羧基（_c〇2H)等名詞 在每一例中亦包含其鹽的形式’例如鹼金屬，鹼土金屬及 銨鹽。雜環基被了解是表示較佳爲含有至少一個選自氮， 硫及氧的雜原子之4-至8-員，飽和或不飽和的環，其例子 爲毗啶基，呋喃基，硫代呋喃基，氧雜環丁烷基 (oxetanyl) ’噻啡基’嗎福林基，六氫口比啡基，卩苔啡基，D比 啡基，硫代派喃基，卩[t唑基，嘧啶基，三啡基，異呋喃 基，呢喃基，六氫吡啶基，甲毗啶基，thiadiazolinyl， thietanyl，三哇基，oxazolanyl，thiolanyl，氮雜肇基，噻π坐 基，異噻唑基，咪唑基或吡咯基。 所使用的硫較佳爲粉末形式。較佳的是，每莫耳苯基 重氮鹽使用1·2至5莫耳，尤其是1.5至3莫耳的硫。 該重氮鹽是以習知方法製備，係藉由$約-5°(：至+5°C 的溫度，將亞硝酸鈉溶液計量供給至相對應的胺的酸性水 溶液中。 「提高的溫度」一詞較佳是表示20至100°C的溫度範 圍。特別有利的是在30至80°C的範圍進行。 合適的水性驗較佳爲一鹼金屬或驗土金屬氫氧化物或 6 本紙張尺度適用中國國家棕準（CNS)A4規格（210 χ 297公釐） ------------------- 訂------- (請先閱讀背面之注意事項再填寫本頁) • A7 1304804 ----------_B7 _____________ 五、發明說明（） ^的水溶液。較佳的是，每莫耳重氮化合物使用2 5 g 5 吴耳，尤其是1.5至3莫耳的鹼。如果式n的苯基重氮鹽 已含有酸基作爲取代基，每個酸基最好需另加入—莫耳的 根據本發明的方法具有一主要的優點，即其可以〜大 的工業規模進行。其步驟通常是在提高的溫度下將硫導入 水性的鹼中’然後將式II之重氮鹽計量供給之。 根據本發明的方法能連續地或閒歇地（不連續地，批 次地）進行’較佳爲間接的操作。間歇的及連續的反應歩 驟兩者都是以在攪拌容器或攪拌容器系列中進行爲較佳。 已發現爲了分離硫醇，藉由加入亞硫酸鈉，亞硫酸氮 鈉或二氧化硫以將過量的硫轉換成硫代硫酸鈉是有利的。 然後將反應溶液酸化。於是硫醇分離出來並且可以從水性 鹽溶液中離析出來。爲了進一步純化，苯硫酚 (phenylthiol)可被蒸飽。 分離出的硫醇的產率一般爲80至100%。反應混合物. 中化學產率通常大於95%。 根據本發明的方法與先前技藝的方法相較具有下列® 點： 、 -它可以大的工業規模進行 -反應步驟簡單，特別是與二硫化物之不同形式比較， 在二硫化物之不同形式下，二硫化物溶液和重氮溶液必須 被同時計量供給至水性的鹼中，以抑制重氮基和氫交換 -不會形成有毒的副產物’特別是不像是在黃原酸鹽的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1304804 . A7 B7 一_____ —-----^ .— "" · ' 五'發明說明（） 方法中，在進行期間會形成莫耳量的cos -與二硫化物及多硫化物的不同形式相較，該反應彳系# 常有選擇性地進行 -所產生的產物之產率高至98% - -能以多用途裝置實行。 根據本發明製備之式I的硫醇特別是用作製備異 呋喃酮型除草劑之中間物，其已描述於，例如US-A-5 717 及 US-A-5 428 002。 後面的實施例進一步的說明本發明。 亶施麗丄7-氫硫基-3-甲基-3H-異苯并呋喃-1-酮的製備 在第一個反應器中，將203克2-胺基-6-U-羥乙基)-苯 甲酸（鈉鹽）以50%水溶液的形式（1.0莫耳）及181克 40%亞硝酸鈉水溶液（1.05莫耳）同時導入428克氫氯酸 (32% )中。在反應完成後，藉由加入氨基磺酸以破壞過 量的亞硝酸鹽。 在第二個反應器中，將800克氫氧化鈉以30%溶液的 形式及71克硫粉末（2.20莫耳）在60°C加熱並攪拌60分 鐘。將在第一個反應器中製備之重氮鹽溶液加至所產生的 混合物，隨著氮的釋出形成對應的硫醇。、 爲了進行實驗，將300克甲苯及195克亞硫酸氫鈉 (0.75莫耳）以40%水溶液的形式加入反應混合物。在8〇 C的溫度，用乙酸將pH g周至8 ’其結果爲苯狀環閉合及過 量的硫被轉換成硫代硫酸鹽。在30°C，進一步將pH降至 6 ’其結果爲’硫醇被游離且爲甲苯相吸收。將甲苯相分離 8 --------I I-----I----訂- - ---- (請先間讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1304804 A7 B7 五、發明說明（ 出，並將5克三苯膦和150克的水加至其中。加熱至約30 t，並將pH調整至11，於是呈鈉鹽形式之苯硫酚被吸收 至水相中，呈鈉鹽形式的7-氫硫基-3-甲基-3H-異苯并呋喃-1-酮可從中分離，產率爲85% (基於2-胺基-6-(1-羥乙基)-苯甲酸）以水溶液的形式。 (請先閱讀背面之注意事項再填寫本頁) ---I I 丨 I 丨訂·1111111- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）
Claims (1)
- Ι30480Ψ :申請專利範圍 1. 一種製備式I之苯硫酣的方法， SH其中 η爲1至.5的整數，及 R爲氣’ Ci.4院基’經基Ci-4院基，Ci_4院胺基，二-C!-4烷胺基，C2_4烯基，C2.4炔基，Cm烷氧基，烷硫 基，苯基，萘基，苯氧基，苯硫基，鹵素，羥基，氫硫 基，羧基，磺酸基，羥胺基或 含有至少一個選自氮、硫 及氧的雜原子之4-至8-員飽和或不飽和的環， 係藉由將式II之苯基重氮鹽 請 閲 讀 背訂i 其中η和R係如所定義的，及X爲鹵素或硫酸氫鹽， 在水性鹼存在下，於在20至100°C的範圍內的溫度下與硫 反應，再分離式I化合物。 2. 根據申請專利範圍第1項之方法，其中每莫耳式II 化合物使用1.2至5莫耳硫粉末。 3. 根據申請專利範圍第2項之方法，其中每莫耳式II 化合物使用1.5至3莫耳硫粉末。 4. 根據申請專利範圍第1至3項中任一項之方法，其 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐) 1304804 * έΐ C8 D8 六、申請專利範圍 '中該溫度範圍係從30至80°C。 5_根據申請專利範圍第1至3項中任一項之方法，其 中每莫耳式II化合物使用1.5至3莫耳水性鹼。 6.根據申請專利範圍第4項之方法，其中每莫耳式Π •化合物使用1.5至3莫耳水性鹼。 2 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH20002000 | 2000-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI304804B true TWI304804B (en) | 2009-01-01 |
Family
ID=4567072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW090124907A TWI304804B (en) | 2000-10-11 | 2001-10-09 | Process for the preparation of thiophenols |
Country Status (21)
| Country | Link |
|---|---|
| US (2) | US20040030135A1 (zh) |
| EP (1) | EP1330434B1 (zh) |
| JP (1) | JP4021760B2 (zh) |
| KR (1) | KR100837098B1 (zh) |
| CN (1) | CN1257156C (zh) |
| AR (1) | AR030866A1 (zh) |
| AT (1) | ATE380790T1 (zh) |
| AU (2) | AU2002221663B2 (zh) |
| BR (1) | BR0114247B1 (zh) |
| CA (1) | CA2423300C (zh) |
| DE (1) | DE60131878T2 (zh) |
| ES (1) | ES2295226T3 (zh) |
| HU (1) | HU228460B1 (zh) |
| IL (2) | IL154804A0 (zh) |
| MX (1) | MXPA03003068A (zh) |
| PL (1) | PL205784B1 (zh) |
| RU (1) | RU2310649C2 (zh) |
| TW (1) | TWI304804B (zh) |
| UA (1) | UA75374C2 (zh) |
| WO (1) | WO2002030883A1 (zh) |
| ZA (1) | ZA200301998B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100697249B1 (ko) * | 2005-12-05 | 2007-03-21 | 주식회사 제이엠씨 | 티오펜올 유도체의 제조방법 |
| CN104829507B (zh) * | 2015-05-06 | 2017-08-18 | 山东豪迈化工技术有限公司 | 无催化剂作用下生产芳香硫酚的方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE433103C (de) * | 1925-02-24 | 1926-08-20 | J G Farbenindustrie Ag | Verfahren zur Darstellung von Mercaptanen der Naphthalinreihe |
| JPS5735858A (en) * | 1980-08-12 | 1982-02-26 | Fuji Photo Film Co Ltd | Color photographic sensitive material |
| JP2990377B2 (ja) * | 1989-10-12 | 1999-12-13 | ノバルティス アクチエンゲゼルシャフト | 複素環式化合物 |
| FR2659738B1 (fr) * | 1990-03-16 | 1993-12-03 | Air Liquide | Procedes colorimetriques de determination et de regulation de la teneur en peracide dans une solution, en presence de peroxyde d'hydrogene. |
| JPH06239856A (ja) * | 1993-02-15 | 1994-08-30 | Shin Nippon Yakuhin Kk | １，３−ベンゾオキサチオール−２−チオン誘導体 |
| US6204293B1 (en) * | 1995-11-06 | 2001-03-20 | University Of Pittsburgh | Inhibitors of protein isoprenyl transferases |
-
2001
- 2001-09-10 UA UA2003054183A patent/UA75374C2/uk unknown
- 2001-10-09 US US10/398,813 patent/US20040030135A1/en not_active Abandoned
- 2001-10-09 AT AT01986676T patent/ATE380790T1/de not_active IP Right Cessation
- 2001-10-09 BR BRPI0114247-0A patent/BR0114247B1/pt not_active IP Right Cessation
- 2001-10-09 AU AU2002221663A patent/AU2002221663B2/en not_active Ceased
- 2001-10-09 HU HU0301353A patent/HU228460B1/hu not_active IP Right Cessation
- 2001-10-09 TW TW090124907A patent/TWI304804B/zh not_active IP Right Cessation
- 2001-10-09 AR ARP010104728A patent/AR030866A1/es not_active Application Discontinuation
- 2001-10-09 PL PL360543A patent/PL205784B1/pl unknown
- 2001-10-09 DE DE60131878T patent/DE60131878T2/de not_active Expired - Lifetime
- 2001-10-09 CA CA002423300A patent/CA2423300C/en not_active Expired - Fee Related
- 2001-10-09 CN CNB018171877A patent/CN1257156C/zh not_active Expired - Lifetime
- 2001-10-09 MX MXPA03003068A patent/MXPA03003068A/es active IP Right Grant
- 2001-10-09 ES ES01986676T patent/ES2295226T3/es not_active Expired - Lifetime
- 2001-10-09 IL IL15480401A patent/IL154804A0/xx active IP Right Grant
- 2001-10-09 AU AU2166302A patent/AU2166302A/xx active Pending
- 2001-10-09 WO PCT/EP2001/011653 patent/WO2002030883A1/en active IP Right Grant
- 2001-10-09 EP EP01986676A patent/EP1330434B1/en not_active Expired - Lifetime
- 2001-10-09 RU RU2003112611/04A patent/RU2310649C2/ru not_active IP Right Cessation
- 2001-10-09 KR KR1020037005019A patent/KR100837098B1/ko not_active IP Right Cessation
- 2001-10-09 JP JP2002534271A patent/JP4021760B2/ja not_active Expired - Lifetime
-
2003
- 2003-03-06 IL IL154804A patent/IL154804A/en not_active IP Right Cessation
- 2003-03-12 ZA ZA200301998A patent/ZA200301998B/en unknown
-
2007
- 2007-03-23 US US11/679,526 patent/US20070161817A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US20070161817A1 (en) | 2007-07-12 |
| CA2423300A1 (en) | 2002-04-18 |
| ES2295226T3 (es) | 2008-04-16 |
| KR100837098B1 (ko) | 2008-06-13 |
| WO2002030883A1 (en) | 2002-04-18 |
| AU2166302A (en) | 2002-04-22 |
| CN1469861A (zh) | 2004-01-21 |
| CN1257156C (zh) | 2006-05-24 |
| 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 |
| UA75374C2 (uk) | 2006-04-17 |
| EP1330434A1 (en) | 2003-07-30 |
| DE60131878T2 (de) | 2008-12-04 |
| RU2310649C2 (ru) | 2007-11-20 |
| JP2004511464A (ja) | 2004-04-15 |
| ZA200301998B (en) | 2004-04-22 |
| KR20030040526A (ko) | 2003-05-22 |
| RU2003112611A (ru) | 2005-01-10 |
| AR030866A1 (es) | 2003-09-03 |
| CA2423300C (en) | 2009-09-29 |
| DE60131878D1 (de) | 2008-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2013506706A5 (zh) | ||
| MY134924A (en) | Process for the industrial synthesis of tetraesters of 5-[bis(carboxymethyl)amino]-3-carboxymethyl-4-cyano-2-thiophenecarboxylic acid, and application to the synthesis of bivalent salts of ranelic acid and their hydrates | |
| TWI304804B (en) | Process for the preparation of thiophenols | |
| Abbasi et al. | One-pot conversion of alkyl halides to organic disulfides (disulfanes) using thiourea and hexamethyldisilazane (HMDS) in DMSO | |
| US4845300A (en) | Synthesis of 2-(perfluoroalkyl) ethanethiols | |
| KR960014099A (ko) | 치환된 벤젠 화합물의 제조방법 | |
| GB619515A (en) | Organic mercury compounds and process for preparing same | |
| KR19990013838A (ko) | 피리딜메틸 이소티오시아네이트의 제조방법 | |
| AU2002221663A1 (en) | Process for the preparation of thiophenols | |
| TW393459B (en) | Process for production of sulfide group-containing mercaptocarboxylic acid and ester thereof | |
| WO2000014060A1 (fr) | Procede de preparation de composes sulfures aromatiques | |
| Jorritsma et al. | The chemistry of small ring compounds. Part 46. Reduction of 1‐halocyclopropyl sulfides by thiolates | |
| JPS62294673A (ja) | Ｎ，ｎ’−ビス〔２，２’−ジチオビス（２−メチルプロパノイル）〕シスチン | |
| JPS5933267A (ja) | グアニジン誘導体およびその製造法 | |
| JPS61145158A (ja) | ４−タ−シヤリ−ブチルベンジルメルカプタンの製造法 | |
| HU193691B (en) | Process for production of organic sulphids and oligosulphids | |
| KR20060097173A (ko) | 친수성 이온성 액체의 제조방법 | |
| KR840004421A (ko) | 4-(치환된 알킬)-n-(1,3-디티올란-2-일리덴) 아닐린의 제조방법 | |
| JPS5877860A (ja) | アミノスルフエニルクロリド誘導体及びその製造法 | |
| JPS6049631B2 (ja) | チオアルコ−ル誘導体およびその製造法 | |
| JPH05178816A (ja) | ハロゲノチオフェノールの製造方法 | |
| O'CONNOR | CLEAVAGE OF DISULFIDES BY PHOSPHORUS NUCLEOPHILES. A SEARCH FOR INTRAMOLECULAR CATALYSIS. | |
| GB725514A (en) | Improvements in or relating to 4(5)-aryloxymethylimidazoles and their preparation | |
| JPH0623178B2 (ja) | ビスアリ−ルチオアルカンの製造方法 | |
| JPS591460A (ja) | ２−メルカプトエチルアミンハロゲン化水素酸塩類の製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |