JPH03197310A - Industrial production of thiophosgene - Google Patents
Industrial production of thiophosgeneInfo
- Publication number
- JPH03197310A JPH03197310A JP1332878A JP33287889A JPH03197310A JP H03197310 A JPH03197310 A JP H03197310A JP 1332878 A JP1332878 A JP 1332878A JP 33287889 A JP33287889 A JP 33287889A JP H03197310 A JPH03197310 A JP H03197310A
- Authority
- JP
- Japan
- Prior art keywords
- thiophosgene
- solution
- reaction
- amount
- pcmm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000009776 industrial production Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- RYFZYYUIAZYQLC-UHFFFAOYSA-N perchloromethyl mercaptan Chemical compound ClSC(Cl)(Cl)Cl RYFZYYUIAZYQLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001923 cyclic compounds Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- LDTGIGXFXUHJNM-UHFFFAOYSA-N 1-methylpyridin-1-ium-2-carboxamide;iodide Chemical compound [I-].C[N+]1=CC=CC=C1C(N)=O LDTGIGXFXUHJNM-UHFFFAOYSA-N 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 6
- -1 cyclic aliphatic hydrocarbon Chemical class 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229910018105 SCl2 Inorganic materials 0.000 abstract 1
- 101001135436 Urodacus yaschenkoi Antimicrobial peptide scorpine-like-2 Proteins 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Ethylcyclopentane Chemical compound CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- QWHNJUXXYKPLQM-UHFFFAOYSA-N dimethyl cyclopentane Natural products CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QEHFDLMARNTXIZ-UHFFFAOYSA-N 1,1-dimethylcyclooctane Chemical compound CC1(C)CCCCCCC1 QEHFDLMARNTXIZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 1
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- FBGUQAGGWLRXTP-UHFFFAOYSA-N ethylcyclooctane Chemical compound CCC1CCCCCCC1 FBGUQAGGWLRXTP-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- POCNHGFJLGYFIK-UHFFFAOYSA-N methylcyclooctane Chemical compound CC1CCCCCCC1 POCNHGFJLGYFIK-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明はチオホスゲンの工業的製法に関する。[Detailed description of the invention] <Industrial application field> The present invention relates to an industrial method for producing thiophosgene.
チオホスゲンは医薬、農薬の合成中間体として非常に有
用である。Thiophosgene is very useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals.
〈従来技術〉
従来の製法としては、パークロロメチルメルカプタン(
以下PCMMと略す)をヨウ素化合物存在下、有機溶媒
−水混合溶媒中、二酸化イオウあるいは硫化水素をガス
状で供給、還元し、チオホスゲンを製造する方法が公知
である(特開昭62−176910号公報)。<Prior art> The conventional manufacturing method involves perchloromethyl mercaptan (
There is a known method for producing thiophosgene by supplying and reducing sulfur dioxide or hydrogen sulfide in gaseous form in an organic solvent-water mixed solvent in the presence of an iodine compound (hereinafter referred to as PCMM) (Japanese Unexamined Patent Publication No. 176910/1982). Public bulletin).
〈従来技術の課題〉
特開昭62−176910号公報に記載された方法にお
いては、二酸化イオウ及び/または硫化水素をガス状で
供給するため、反応液に溶解されなかった余剰の該ガス
が反応器外に流出する。こにため、該ガスの流出に同伴
し、目的物のチオホスゲンが反応器外に放出され、収率
の低下をきたす。また、大量スケールで実施した場合、
チオホスゲンの反応器からの流出は非常に危険である。<Problems with the Prior Art> In the method described in JP-A No. 62-176910, sulfur dioxide and/or hydrogen sulfide are supplied in gaseous form, so excess gas that is not dissolved in the reaction liquid is reacted. Spills out of the container. Therefore, the target product, thiophosgene, is released out of the reactor along with the outflow of the gas, resulting in a decrease in yield. Also, when carried out on a large scale,
Escape of thiophosgene from the reactor is very dangerous.
さらに、同特許記載の有機溶媒としては、四塩化炭素、
ジクロロメタン、クロロホルム、ジクロロエタン等のハ
ロゲン化炭化水素溶媒、ベンゼン等の芳香族炭化水素溶
媒であり、ハロゲン化炭化水素溶媒は、近年毒性問題が
指摘され、環境汚染等関連法規制で取扱い基準が厳くな
ってきている。Furthermore, the organic solvents described in the patent include carbon tetrachloride,
These include halogenated hydrocarbon solvents such as dichloromethane, chloroform, and dichloroethane, and aromatic hydrocarbon solvents such as benzene. In recent years, toxicity problems have been pointed out for halogenated hydrocarbon solvents, and handling standards have become stricter under laws and regulations related to environmental pollution. It has become to.
一方、ベンゼン等の芳香族炭化水素溶媒は、反応原料で
あるPCMMが過塩素化物であるために、反応溶媒とし
て使用した場合、毒性の高い塩素化芳香族炭化水素を副
生する恐れがある。On the other hand, when aromatic hydrocarbon solvents such as benzene are used as reaction solvents, there is a risk of producing highly toxic chlorinated aromatic hydrocarbons as by-products since PCMM, which is a reaction raw material, is a perchlorinated product.
く課題を解決するための手段〉
本発明者らは、チオホスゲンの工業的かつ安全な製法に
ついて鋭意検討した結果、触媒存在下、PCMMの脂肪
族炭化水素溶媒に亜硫酸水溶液を供給し反応させること
により、二酸化イオウ及び/または硫化水素をガス状で
供給し反応させる場合と比較して、反応による発熱が小
さく、また余剰の二酸化イオウの系外への流出がなく、
高収率でしかも安全にチホスゲンを製造できることを見
出だした。Means for Solving the Problems> As a result of intensive study on an industrial and safe production method for thiophosgene, the present inventors discovered that by supplying an aqueous sulfite solution to an aliphatic hydrocarbon solvent of PCMM in the presence of a catalyst and causing the reaction. , compared to the case where sulfur dioxide and/or hydrogen sulfide are supplied in gaseous form and reacted, the heat generated by the reaction is small, and excess sulfur dioxide does not flow out of the system.
It has been discovered that typhosgene can be produced safely with high yield.
さらに反応溶媒として使用する脂肪族炭化水素溶媒は、
ハロゲン化炭化水素溶媒と比較して毒性が低く、また安
定で、反応に同等悪影響を与えないことを見出だした。Furthermore, the aliphatic hydrocarbon solvent used as a reaction solvent is
It has been found that it is less toxic and stable than halogenated hydrocarbon solvents, and does not have the same adverse effect on reactions.
加えて、反応により得られるチオホスゲンに混入する不
純物は、脂肪族炭化水素に対して溶解度が低く、さらに
水に溶解または水で分解するが、チオホスゲンは、水に
対して比較的安定でしかも水に殆ど溶解しないことを見
出だし本発明を完成させるに至った。In addition, impurities mixed into the thiophosgene obtained by the reaction have low solubility in aliphatic hydrocarbons and dissolve in or decompose in water, but thiophosgene is relatively stable in water and does not dissolve in water. They discovered that it hardly dissolves and completed the present invention.
即ち、本発明は、
(1)パークロロメチルメルカプタンの脂肪族炭化水素
溶媒溶液に、触媒存在下、亜硫酸水溶液を供給し反応さ
せ得られる反応液を分液の後、生成するチオホスゲンに
対して1重量倍量以上の水で洗浄することを特徴とする
チオホスゲンの工業的製法。That is, the present invention provides: (1) A sulfurous acid aqueous solution is supplied to a solution of perchloromethyl mercaptan in an aliphatic hydrocarbon solvent in the presence of a catalyst, and the resulting reaction solution is separated, and then 1 An industrial method for producing thiophosgene, characterized by washing with water in an amount equal to or more than twice its weight.
(2)触媒が、一塩化イオウ、二塩化イオウ、アルカリ
金属ヨウ化物及びヨウ素のうち一種または二種以上の混
合物であることを特徴とする特許請求範囲第(1)項に
記載の方法。(2) The method according to claim (1), wherein the catalyst is one or a mixture of two or more of sulfur monochloride, sulfur dichloride, alkali metal iodide, and iodine.
(3)脂肪族炭化水素溶媒が炭素数5〜15よりなる、
直鎖、分岐または環状化合物であることを特徴とする特
許請求範囲第(1)項に記載の方法を提供するものであ
る。(3) the aliphatic hydrocarbon solvent has 5 to 15 carbon atoms;
The present invention provides a method according to claim (1), characterized in that the compound is a linear, branched or cyclic compound.
く作用〉 以下、本発明の詳細な説明する。Effect〉 The present invention will be explained in detail below.
本発明の方法は、反応器に予めPCMM並びに脂肪族炭
化水素を仕込み、これに亜硫酸水溶液を供給し反応させ
る。触媒の添加は、通常反応開始前に予め反応器に仕込
むが、PCMMの脂肪族炭化水素溶媒に対して溶解性の
低いアルカリ金属ヨウ化物は固体のまま反応器に仕込ん
でも良いし、また供給する亜硫酸水溶液に溶解させて本
反応に用いても同等支障はない。In the method of the present invention, PCMM and aliphatic hydrocarbon are charged in advance into a reactor, and an aqueous sulfurous acid solution is supplied thereto for reaction. The catalyst is usually added to the reactor in advance before the reaction starts, but the alkali metal iodide, which has low solubility in the aliphatic hydrocarbon solvent of PCMM, may be added to the reactor as a solid, or it can be fed. Even if it is dissolved in an aqueous sulfite solution and used in this reaction, there is no problem.
本発明に使用する脂肪族炭化水素溶媒としては、炭素数
5〜15からなる直鎖、分岐または環状化合物であれば
あらゆるものが使用可能であるが、工業的に入手可能な
、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、
デカン、ウンデカン、ドデカン、トリデカン等の直鎖脂
肪族炭化水素、ジメチルブタン、メチルペンタン、ジメ
チルペンタン、メチルヘキサン、トリメチルペンタン、
ジメチルヘキサン、メチルへブタン等の分岐脂肪族炭化
水素、シクロペンタン、シクロヘキサン、シクロへブタ
ン、シクロオクタン、メチルシクロペンタン、メチルシ
クロヘキサン、メチルシクロへブタン、メチルシクロオ
クタン、ジメチルシクロペンタン、ジメチルシクロヘキ
サン、ジメチルシクロへブタン、ジメチルシクロオクタ
ン、エチルシクロペンタン、エチルシクロヘキサン、エ
チルシクロへブタン、エチルシクロオクタン等の環状脂
肪族炭化水素、混合物として、石油エーテル、石油ベン
ジン、リグロイン等があげられるが、好ましくは工業的
に容易に入手可能なものとして、ペンタン、ヘキサン、
ヘプタン、オクタン、シクロヘキサン、石油エーテル、
石油ベンジン、リグロインである。As the aliphatic hydrocarbon solvent used in the present invention, any linear, branched or cyclic compound having 5 to 15 carbon atoms can be used, including industrially available pentane, hexane, heptane, octane, nonane,
Straight chain aliphatic hydrocarbons such as decane, undecane, dodecane, tridecane, dimethylbutane, methylpentane, dimethylpentane, methylhexane, trimethylpentane,
Branched aliphatic hydrocarbons such as dimethylhexane, methylhebutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, methylcyclopentane, methylcyclohexane, methylcyclohebutane, methylcyclooctane, dimethylcyclopentane, dimethylcyclohexane, dimethylcyclo Cycloaliphatic hydrocarbons such as hebutane, dimethylcyclooctane, ethylcyclopentane, ethylcyclohexane, ethylcyclohebutane, and ethylcyclooctane, and mixtures such as petroleum ether, petroleum benzine, and ligroin, are preferably used industrially. Easily available pentane, hexane,
heptane, octane, cyclohexane, petroleum ether,
Petroleum benzine and ligroin.
脂肪族炭化水素溶媒中のPCMMの濃度はあらゆる濃度
で実施可能であるが、経済性並びに、反応制御の容易さ
等の理由で、10〜70wt%の濃度範囲とすることが
好ましい。Although any concentration of PCMM in the aliphatic hydrocarbon solvent can be used, it is preferably in the range of 10 to 70 wt % for reasons such as economic efficiency and ease of reaction control.
本発明に使用する触媒としては、一塩化イオウ、二塩化
イオウ、アルカリ金属ヨウ化物並びにヨウ素であるが、
各々単独で用いても良いしまた、二種以上の混合物とし
て使用しても良い。アルカリ金属ヨウ化物としてはあら
ゆるものが使用可能であるが、好ましくはヨウ化カリウ
ム、ヨウ化ナトリウムである。Catalysts used in the present invention include sulfur monochloride, sulfur dichloride, alkali metal iodides, and iodine.
Each may be used alone or as a mixture of two or more. Any alkali metal iodide can be used, but potassium iodide and sodium iodide are preferred.
触媒の添加量は反応に供すPCMMに対して、あらゆる
濃度で可能であるが、余りにも少量では反応速度が小さ
く工業的ではなく、また大量の使用は反応速度に顕著な
効果が見られないため経済的ではない。このため、触媒
の添加量は、一種または二種以上の混合物として、PC
MMに対して0.3〜5.0m01%の範囲が好ましい
。The amount of catalyst added can be any concentration relative to the PCMM used for the reaction, but if it is too small, the reaction rate is too low to be industrially practical, and if it is used in a large amount, there will be no noticeable effect on the reaction rate. It's not economical. For this reason, the amount of catalyst added is determined by adding one type or a mixture of two or more types.
The range of 0.3 to 5.0 m01% based on MM is preferable.
反応に使用する亜硫酸水溶液の濃度は5、水に対する、
二酸化イオウの飽和溶解度以下であればあらゆる濃度で
可能であるが、水溶液中濃度が4wt%以下では、供給
液量が大となり経済的ではなく、また飽和溶解量では、
反応により副生する硫酸並びに塩酸により、二酸化イオ
ウのガスが発生し、反応器外へ流出し、これに同伴して
、目的物チオホスゲンの流出が発生する場合があるため
、好ましくは、水溶液中濃度4 w t%以上でなおか
つ飽和溶解量の90wt%以下である。The concentration of the sulfite aqueous solution used in the reaction is 5, relative to water,
Any concentration is possible as long as it is below the saturation solubility of sulfur dioxide, but if the concentration in the aqueous solution is below 4 wt%, the amount of liquid to be supplied will be large, making it uneconomical.
Sulfur dioxide gas is generated by the sulfuric acid and hydrochloric acid produced as by-products of the reaction, and flows out of the reactor. This may cause the target product thiophosgene to flow out. Therefore, it is preferable to reduce the concentration in the aqueous solution. It is 4 wt% or more and 90 wt% or less of the saturated dissolution amount.
また、亜硫酸の供給量はPCMMに対して、等モル以上
であれば良いが、余りにも過剰の使用は生成したチオホ
スゲンの分解が発生する場合があり好ましくなく、1.
1倍モル量未満では、原料のPCMMが残存する場合が
ある。このため、好ましくは、1.1倍モル量以上〜3
.0倍モル量の範囲である。Further, the amount of sulfite to be supplied may be equal to or more than equimolar to PCMM, but using too much excess may cause decomposition of the generated thiophosgene, which is not preferable.
If the amount is less than 1 times the molar amount, the raw material PCMM may remain. For this reason, preferably 1.1 times or more molar amount to 3
.. The range is 0 times the molar amount.
反応温度としては、−10〜40’Cでなおかつ使用す
る脂肪族炭化水素溶媒の沸点以下であれば可能であるが
、0℃では水の凝結が発生する場合があり、20℃以上
では反応に供する亜硫酸水溶液中の二酸化イオウの飽和
溶解度が低下し、PcMMとの反応に必要な亜硫酸水溶
液の液量が大となり好ましくない。従って、反応温度は
、5℃以上、20℃以下が好ましい。The reaction temperature can be -10 to 40'C and below the boiling point of the aliphatic hydrocarbon solvent used, but at 0°C water may condense, and at 20°C or higher the reaction will not proceed. The saturated solubility of sulfur dioxide in the aqueous sulfite solution provided decreases, and the amount of the aqueous sulfite solution required for reaction with PcMM becomes large, which is not preferable. Therefore, the reaction temperature is preferably 5°C or higher and 20°C or lower.
亜硫酸水溶液の供給速度は、供給速度を大とすることに
より、短時間で反応を完結させることが可能であるが、
単位時間あたりの発熱量が大となるため、所定の温度で
反応を実施できる供給速度とすることが好ましい。The reaction can be completed in a short time by increasing the supply rate of the sulfite aqueous solution, but
Since the amount of heat generated per unit time is large, it is preferable to set the feed rate to such a rate that the reaction can be carried out at a predetermined temperature.
亜硫酸水溶液の供給後、通常、さらに2〜24時間の熟
成を行うことにより、反応は完結する。After the aqueous sulfite solution is supplied, the reaction is usually further aged for 2 to 24 hours to complete the reaction.
反応終了後、チオホスゲンを含む混合液は静定し、分液
の後、さらに、生成したチオホスゲンに対して1重量倍
量以上の水で洗浄する。After the reaction is completed, the mixed solution containing thiophosgene is allowed to settle, and after separation, the mixture is further washed with water in an amount equal to or more than 1 times the weight of the produced thiophosgene.
洗浄水量はあらゆる量比で可能であるが、1重量倍量以
下では分液操作が困難であり、10重量倍量以上では特
別の利益はもたらさない。洗浄回数としては1回でも良
いし、また数回に分けて実施しても同等支障はない。The amount of washing water can be adjusted to any ratio, but if the amount is less than 1 times the amount by weight, the liquid separation operation will be difficult, and if the amount is more than 10 times the amount by weight, no special benefits will be brought about. The number of times of cleaning may be one time, or it may be divided into several times without any problem.
く効果〉
本発明は、高収率でしかも安全なチオホスゲンの工業的
製法を提供する。Effects> The present invention provides a high-yield and safe industrial method for producing thiophosgene.
〈実施例〉
以下、実施例により本発明を具体的に説明するが本発明
はこれ等実施例のみに限定されるものではない。<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
なお、本実施例において不純物塩化イオウ類の分析はガ
スクロマトグラフィーで行い、ヨウ素イオンは、イオン
クロマトグラフィーにより行った。In this example, the impurity sulfur chloride was analyzed by gas chromatography, and the iodine ion was analyzed by ion chromatography.
〔実施例1〕
撹拌機を備えた冷却ジャケット付き100pのグラスラ
イニング反応装置に、水51.CN!を仕込み、撹拌し
ながら二酸化イオウ5.6kgをボンベよりガス状でバ
ブリングさせながら供給、溶解させ、得られた亜硫酸水
溶液は抜出し、供給タンクへ移液した。[Example 1] A 100p glass-lined reactor with a cooling jacket equipped with a stirrer was charged with 51% of water. CN! While stirring, 5.6 kg of sulfur dioxide was supplied and dissolved in gaseous form from a cylinder while stirring, and the resulting aqueous sulfurous acid solution was extracted and transferred to a supply tank.
次いで、反応装置を水で洗浄の後、ベントラインにアニ
リン2.0kg並びに四塩化炭素3. 0kgを仕込ん
だチオホスゲントラップを取付け、次いでPCMMlo
、8kg、ヨウ化カリウム固体77゜1g並びにシクロ
ヘキサン21.6kgを仕込み、撹拌しながら冷却し、
温度を10℃とした。これに、前記調製した亜硫酸水溶
液を3時間かけて供給の後、さらに12℃で6時間反応
を行った。Next, after washing the reactor with water, 2.0 kg of aniline and 3.0 kg of carbon tetrachloride were added to the vent line. Install a thiophosgene trap loaded with 0 kg, then
, 8 kg, potassium iodide solid 77°1 g and 21.6 kg of cyclohexane were charged, and cooled while stirring.
The temperature was 10°C. After supplying the sulfurous acid aqueous solution prepared above over a period of 3 hours, the reaction was further carried out at 12° C. for 6 hours.
反応液を静定、分液後、次いで水7gを添加し、再度撹
拌し、洗浄を行った。After the reaction solution was stabilized and separated, 7 g of water was added, stirred again, and washed.
洗浄後、分液しチオホスゲン溶液を得、ガスクーロマド
グラフィーで分析の結果、チオホスゲン収量6. 5k
g、収率97.3%、PCMM転化率100%で、チオ
ホスゲン溶液中のヨウ素イオン濃度は、32ppmであ
った。After washing, the thiophosgene solution was separated and analyzed by gas coulomadography, and the yield of thiophosgene was 6. 5k
g, yield 97.3%, PCMM conversion rate 100%, and the iodine ion concentration in the thiophosgene solution was 32 ppm.
また、ベントトラップを分析の結果、チオホスゲンの飛
散は認めれれなかりた。Furthermore, as a result of analyzing the vent trap, no thiophosgene was found to be scattered.
〔実施例2〜5〕
実施例1と同じ装置で、表1中に示した条件下反応を行
った。[Examples 2 to 5] Reactions were carried out using the same apparatus as in Example 1 under the conditions shown in Table 1.
結果を表1に示した。The results are shown in Table 1.
〔比較例1〜3〕
実施例1と同じ装置で表1中に示した条件下反応を行っ
た。[Comparative Examples 1 to 3] Reactions were carried out using the same apparatus as in Example 1 under the conditions shown in Table 1.
結果を表1中に示した。The results are shown in Table 1.
Claims (3)
溶媒溶液に、触媒存在下、亜硫酸水溶液を供給し反応さ
せ得られる反応液を分液の後、生成するチオホスゲンに
対して1重量倍量以上の水で洗浄することを特徴とする
チオホスゲンの工業的製法。(1) In the presence of a catalyst, an aqueous sulfurous acid solution is supplied to a solution of perchloromethyl mercaptan in an aliphatic hydrocarbon solvent, and the resulting reaction solution is separated. An industrial method for producing thiophosgene, which is characterized by washing with.
金属ヨウ化物及びヨウ素のうち一種または二種以上の混
合物であることを特徴とする特許請求範囲第(1)項に
記載の方法。(2) The method according to claim (1), wherein the catalyst is one or a mixture of two or more of sulfur monochloride, sulfur dichloride, alkali metal iodide, and iodine.
直鎖、分岐または環状化合物であることを特徴とする特
許請求範囲第(1)項に記載の方法。(3) the aliphatic hydrocarbon solvent has 5 to 15 carbon atoms;
The method according to claim (1), wherein the compound is a linear, branched or cyclic compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1332878A JP2808764B2 (en) | 1989-12-25 | 1989-12-25 | Industrial production of thiophosgene. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1332878A JP2808764B2 (en) | 1989-12-25 | 1989-12-25 | Industrial production of thiophosgene. |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03197310A true JPH03197310A (en) | 1991-08-28 |
JP2808764B2 JP2808764B2 (en) | 1998-10-08 |
Family
ID=18259811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1332878A Expired - Fee Related JP2808764B2 (en) | 1989-12-25 | 1989-12-25 | Industrial production of thiophosgene. |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2808764B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113860308A (en) * | 2021-09-15 | 2021-12-31 | 爱斯特(成都)生物制药股份有限公司 | Method for continuously preparing thiophosgene by using sulfur dioxide |
-
1989
- 1989-12-25 JP JP1332878A patent/JP2808764B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113860308A (en) * | 2021-09-15 | 2021-12-31 | 爱斯特(成都)生物制药股份有限公司 | Method for continuously preparing thiophosgene by using sulfur dioxide |
CN113860308B (en) * | 2021-09-15 | 2023-01-10 | 爱斯特(成都)生物制药股份有限公司 | Method for continuously preparing thiophosgene by using sulfur dioxide |
Also Published As
Publication number | Publication date |
---|---|
JP2808764B2 (en) | 1998-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0119274B1 (en) | Process for producing aminoalkylsulfonic acids | |
CN103508880A (en) | Method for synthesizing 3,5-dichlorobenzoyl chloride | |
RU2765715C2 (en) | Composition for deoxyfluorination | |
JPH0532610A (en) | Production of 1,2-naphthoquinone diazido-5-sulfonyl chloride | |
JPH03197310A (en) | Industrial production of thiophosgene | |
US4372938A (en) | Producing sulfur tetrafluoride using amine/hydrogen fluoride complex | |
US3544625A (en) | Method for producing perchloromethyl mercaptan | |
JP2808696B2 (en) | Method for producing thiophosgene | |
EP0849253B1 (en) | Process for producing benzoyl chlorides | |
JP2808697B2 (en) | Industrial production of thiophosgene | |
JP2808695B2 (en) | Preparation of thiophosgene | |
EP0844239B1 (en) | Method for producing homocystine | |
JPH0337110A (en) | Production of thiophosgene | |
JP3882855B2 (en) | Method for producing alkylbenzoyl chloride | |
JP2003104951A (en) | Method for producing perfluoroaklylsulfonyl halide | |
JP2712694B2 (en) | Process for producing phenylchlorothioformates | |
JP2625850B2 (en) | Method for producing thiophosgene | |
DE69811358T2 (en) | METHOD FOR PRODUCING 1-CHLOROCARBONYL-4-PIPERIDINOPIPERIDINE OR THE HYDROCHLORIDE THEREOF | |
JPH0211559A (en) | Production of disulfide | |
US4469884A (en) | Preparation of n-methoxy-n-methylurethanes | |
US3386903A (en) | Method for preparing oximinomethyl benzoic acid | |
SK162996A3 (en) | Method for producing thioglycolic acid | |
JPS62190157A (en) | Manufacture of sulfonyl chloride | |
JP3788482B2 (en) | Method for producing alkylbenzoyl chloride | |
US4401639A (en) | Preparation of carbonyl cyanide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070731 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080731 Year of fee payment: 10 |
|
LAPS | Cancellation because of no payment of annual fees |