CN102372738A - Application of LJ reaction in preparation of wittig reagent and glufosinate-ammonium - Google Patents

Application of LJ reaction in preparation of wittig reagent and glufosinate-ammonium Download PDF

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CN102372738A
CN102372738A CN2010102581434A CN201010258143A CN102372738A CN 102372738 A CN102372738 A CN 102372738A CN 2010102581434 A CN2010102581434 A CN 2010102581434A CN 201010258143 A CN201010258143 A CN 201010258143A CN 102372738 A CN102372738 A CN 102372738A
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李坚
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Purpana Beijing Technologies Co Ltd
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Abstract

The present invention relates to an application of a new LJ intramolecular isomerization reaction in preparation of a wittig reagent and a herbicide of glufosinate-ammonium. With the application, a new approach of a synthesis route for preparing the wittig reagent and the glufosinate-ammonium is developed, the disadvantages of the existing wittig reaction are improved, and the industrial design of the glufosinate-ammonium production is improved.

Description

LJ is reflected at the application in preparation Witting reagent and the careless ammonium phosphine
The present invention relates to a kind of LJ intramolecularly isomery new reaction; Application in Wittig phosphonate reagent and weedicide grass ammonium phosphine; The new way of preparation Witting reagent and careless ammonium phosphine synthetic route has been opened up in this application; Improve the shortcoming that original Wittig reaction exists, improved the industrial design that careless ammonium phosphine is produced.
Background technology
On July 18th, 2010; Patent applicant of the present invention has applied for that application number is 201010237200.0, the patent of invention of title " LJ isomerization reaction "; That time application has been omitted many contents in the application facet of relevant LJ reaction, this time is through patented claim again it to be filled.Wittig reaction is one of most important reaction that is used to form in the organic chemistry on the two keys of carbon one carbon; This reaction is gained the name in German organic chemist George Wittig of this reaction being made outstanding contribution; He has shared Nobel chemistry Prize in 1979 with Americanized scholar HCBrown; Prize-winning reason is that he develops into the important reagent in the organic synthesis to phosphorus compound, and this discovery can be widely used on synthesizing of drug molecule and organic cpds.But from the viewpoint that modern industrialization is implemented, also there are two main shortcomings in Wittig reaction: after (1) reaction finished, the phosphorus oxide by product of generation can be dissolved in organic solvent and cause the separation and purifying inconvenience of product; (2) although the Wittig reaction productive rate is higher, its atom utilization is very low, does not meet the principle of modern process for cleanly preparing; For example; In the Wittig reaction by the participation of Diethylaminoethyl triphenyl phosphorus molecule, only there is methylene radical to be utilized in the product, has only 14 parts of quality to be utilized in 356 parts of quality of reagent molecule; Utilization ratio only has 4%, but also has produced " refuse " triphenylphosphine oxide of 278 parts of quality.
Summary of the invention
The objective of the invention is to use a kind of LJ reaction of China's independent development; The new way of preparation Witting reagent is provided, especially under non-alkaline condition, also can prepares required Wittig novel agent by highly selective, when carrying out Wittig reaction with this; The by-product inorganic phosphide; For example POCl3 was both separated it easily from the organic reaction system, can utilize it to prepare various organo phosphorous compoundss again; Atom utilization is generally 90～100%, and the industrializing implementation of Wittig reaction is significant.
1, LJ is reflected at the application in the preparation Witting reagent
Wittig reaction is a very important organic reaction, in organic synthesis, has irreplaceable status, and five during the last ten years, still in organic synthesis, is bringing into play very important effect so far.Prepare new Witting reagent, for the improvement of Wittig reaction, especially for the additional and expansion of asymmetric Wittig reaction, have important effect, LJ is reflected at the application of this respect, has very great value.
1.1 the preparation of classical Witting reagent is to generate season
Figure BSA00000237064100021
salt through triphenylphosphine and methyl bromide; Under the alkali effect, lose a part hydrogen halide then and make, a representes with formula:
Figure BSA00000237064100022
(a) 1 being Witting reagent in the formula, is a crucial midbody of Wittig reaction, and an essential condition of its reaction mechanism is must be under alkaline condition.
The principle of LJ reaction is: if can with the element (for example C, S, N, O) of P (perhaps B) Cheng Shuanjian; On P (or B), be connected with strong electron-withdrawing group group, and be connected with simultaneously alkyl or-S-or-NHR or-during groups such as O-, it improves 10～20 times when becoming the specific activity of two keys to be connected with electron donating group with P; The activity that the phosphine of three-fold coordination simultaneously thing is converted into four-coordination phosphine thing becomes multiple to increase; Note, because of become the active order of two keys with P: O＞S＞N＞C, so can not contain O in the used alkali reagent; The S atom, otherwise can not generate Witting reagent.For example, under anhydrous and no oxygen condition, methyl dichloro phosphorus is heated up (in 50 ℃), the intramolecularly isomery becomes new a kind of Witting reagent 2, and is as follows:
The 2nd, the innovation compound, a kind of new Witting reagent, itself and aldehydes or ketones reaction can generate olefin(e) compound,
Figure BSA00000237064100032
It is consistent to carry out the effect of Wittig reaction with 2 and 1, can obtain identical product 3, but wide application value is more arranged; Because of the boiling point of by product 4 is lower, belong to inorganic phosphide again, than the by product triphenylphosphine oxide of classical Wittig reaction separate easily more; Particularly two active chlorine atoms are arranged on 4; Be the important source material that is easy to prepare many organo phosphorous compoundss, for example, it is the important source material of preparation Glyphosate 62 IPA Salt:
4+CH 2＝N-CH 2CN——→
Figure BSA00000237064100041
So; Adopt the principle of LJ reaction, become multiple to increase activity, no matter be the new Witting reagent of preparation for a HX molecule of sloughing season on
Figure BSA00000237064100042
salt; Still prepare classical Witting reagent; Can under acidic conditions, be not that certain requirement is carried out diphenyl phosphine chloride at " under the alkaline condition " yet; Phenylphosphonic dichloride is identical with triphenylphosphine, can become the basic raw material of preparation Witting reagent:
Figure BSA00000237064100043
Among the formula C, X representes halogen atom, phenyl; H; Z representes halogen atom, phenyl, H; Wait other not contain O, all electron-withdrawing groups of S atom; R representes all alkylates,
One of classical reaction comprises the several steps of following order:
Figure BSA00000237064100045
Figure BSA00000237064100046
Figure BSA00000237064100051
Above-mentioned reaction also can A, B, C, D step merge into a step cascade reaction.
1.2 LJ reaction principle (part) is as follows:
The four-coordination phosphine (phosphorus) that contains groups such as
Figure BSA00000237064100052
is changed thing; Under alkaline condition; Have with P on rightabout effect when being connected with electron-withdrawing group; Alkalescence is strong more, and this effect is big more, promptly has the four-coordination compound to be converted into the trend of three-fold coordination compound; For non-phosphine thing; This trend just becomes set, such as, phosphorous acid and dimethylphosphite exist with four-coordination " set " under acidic conditions; At alkaline condition; Comprise that its basic salt but exists with three-fold coordination " set ", phosphorous acid ester can not exist under acidic conditions naturally, and these can be in the LJ reaction molecular obtain explanation the rule of isomery.Just because of this; (1) group changes and is that the trend of (2), (3), (4) group, (2) group change and is the trend of (3), (4) group, causes (4) group that the trend that becomes carbanion is arranged; Alkalescence is big more; This trend is strong more, and this LJ reaction principle has important effect in the Wittig-Horner reaction, in preparation Wittig-Horne reagent, has important use to be worth.
Every having
Figure BSA00000237064100053
The phosphorus of group (phosphine) compound has strong electron-withdrawing group on its alpha-carbon atom simultaneously, as-CX 3,-CN, trichlorophenyl, nitrophenyl etc., under strong alkaline condition, change is the trend of the two keys of phosphorus carbon to the two keys of phosphorus oxygen (or the two keys of phosphorus nitrogen), changing is the trend of α-C negative ion.(5) R and R and in (6) formula 1And R 2Be the group that can not react with highly basic, R 2Be alkynylene, R and R 1The expression alkyl, alkoxyl group, or contain H 2The N-group compound,
Figure BSA00000237064100061
10 is new Wittig-Horner reagent in the formula (d), with formula (5) or formula (6) phosphorus (phosphine) compound, prepares new Wittig-Horner reagent, comprises the several steps of following order:
A selects
Figure BSA00000237064100062
12 or 13 compounds meet following prerequisite:
R or R 1Or Z can not with highly basic generation chemical reaction, perhaps can be not under preparation process condition and highly basic generation chemical reaction;
Z representes strong electron-withdrawing group group in 12 and 13, and trichlorophenyl, nitrophenyl, halogen atom are arranged-CN; Or the like;
14 and 15 expression Wittig-Horner reagent general formulas, M representes highly basic in the following formula, and NaH is for example arranged, PhLi, NaNH 2, C 2H 5ONa, NaOH-EtOH etc.
1.3LJ be reflected at the application in the asymmetric Wittig reaction
According to the principle of LJ reaction, the instance of the asymmetric Wittig reaction of analysis of classical, can release following rule:
1.3.1 be connected with electron-withdrawing group on the P atom of Witting reagent, its sucting electronic effect is big more, then Witting reagent is more unstable, but the reactive behavior of preparation Witting reagent is big more under acidic conditions; So under non-alkaline condition, also can the season phosphonium salt be prepared into Witting reagent;
1.3.2 be connected with electron-withdrawing group on the Witting reagent phosphorus atom, its stereoselectivity mainly generates Z-type alkene, its sucting electronic effect is strong more, and the selectivity that generates Z-type alkene is just high more; Otherwise, being connected with electron donating group on the Witting reagent phosphorus atom, its stereoselectivity mainly generates E-type alkene, and it is strong more that it pushes away electronic effect, and the selectivity that generates E-type alkene is just high more;
1.3.3 the mechanism of Wittig reaction is at first Wittig reagent and aldehyde, ketone generation addition reaction; Directly form phosphorus oxa-four membered ring; Then according to the rule of LJ intramolecularly isomerization reaction, the vibration or the rotation of the key that forms through the atom that links to each other with P cause this phosphorus oxa-four membered ring cracking; Or cause this pentacoordinate phosphine thing and change four-coordination phosphine thing into, finally resolve into olefin(e) compound.
The rule of LJ intramolecularly isomerization reaction is described below, by the bond energy size order:
Figure BSA00000237064100081
Wherein, More than the big integral multiple of bond energy of the bond energy of two keys of phosphorus oxygen and the two keys of phosphorus sulphur than two keys of phosphorus nitrogen and the two keys of phosphorus carbon; So under acidic conditions; On phosphorus atom, be connected with electron-withdrawing group; And be connected with simultaneously O or S or N or C atomic time; The trend that has
Figure BSA00000237064100082
direction to transform, otherwise, under alkaline condition; On phosphorus atom, be connected with electron donating group and be connected with O or S or N or C atomic time simultaneously, the trend that has
Figure BSA00000237064100083
direction to transform.
So can be derived by above-mentioned LJ reaction " trend ": Witting reagent or phosphorus imines ylide reagent also all can react with the compound that contains
Figure BSA00000237064100084
group and generate olefin(e) compound or constitute the C=N compound;
(1) new Wittig reaction route
(2) new Aza-Wittig reaction scheme
Figure BSA00000237064100091
Above-mentioned rule is to have purpose to prepare the industrial design that new Witting reagent is used for asymmetric Wittig reaction to have opened up many new thinkings, particularly has important effect for synthetic new optically active Witting reagent that has.
1.4 LJ is reflected at the application in the Aza-Wittig reaction
1.4.1 the preparation of traditional phosphorus imines ylide reagent all is to select the reaction of triazo-compound and three-fold coordination phosphine thing for use, adopts the LJ reaction method, can select for use with the triazo-compound corresponding compounds (only be with N 3-group makes into
Figure BSA00000237064100092
Or H 2The N-group); With the phosphorus trihalide reaction that is connected with strong electron-withdrawing group group on the phosphorus atom, can reach the purpose of the similar phosphorus imines ylide reagent of preparation, the yield of this reaction is greater than 98%; Has higher selectivity; And,, has bigger using value for industrializing implementation for process for cleanly preparing with the alternative triazo-compound of aminated compounds.
The LJ reaction:
27 is a kind of new phosphorus imines ylide reagent, and R representes various alkylates.
1.4.2 according to the LJ reaction principle, the rule of above-mentioned 1.3.1 and 1.3.2,1.3.3 is equally applicable to asymmetric Aza-Wittig reaction, has the meaning of no less important for the preparation of photolytic activity phosphorus imines ylide reagent.
2LJ is reflected at the application in the careless ammonium phosphine of preparation
Grass ammonium phosphine is by the development of Japanese agricultural chemicals company, with the weedicide of the common exploitation of Bayer AG, has very wide development prospect; But defectives such as existing synthesis route exists reaction preference low, and economy is low, and wastewater discharge is big; Adopt the LJ reaction method, can reach the standard of process for cleanly preparing.
2.1. careless ammonium phosphine is synthetic, comprises the several steps of following order:
A LJ reaction
Figure BSA00000237064100101
16,17,18 are the innovation compound
Figure BSA00000237064100102
C, the reaction of Shi Te Rec
Figure BSA00000237064100103
R representes in the formula: H,
Figure BSA00000237064100111
Figure BSA00000237064100112
2.2 careless ammonium phosphine is synthetic, comprises the several steps of following order:
A LJ reaction
Figure BSA00000237064100113
21 are the innovation compound,
20+ tetramethyl plumbane or trimethylaluminium-→ 21
29+H 2O or air---→ 18
B, identical with the 2.1B step
C, identical with the 2.1C step
D, identical with the 2.1D step
2.3 careless ammonium phosphine is synthetic, comprises the several steps of following order
The reaction of A Shi Te Rec
Figure BSA00000237064100121
R representes
Figure BSA00000237064100122
H in the formula,
22 are the innovation compound
Figure BSA00000237064100123
C, existing bibliographical information, 23 and 24 all is the midbody of the careless ammonium phosphine of preparation, methylate and hydrolysis after promptly transform into careless ammonium phosphine;
Specific embodiments
Embodiment 1
Molecule proportioning phosphorus trichloride: methyl chloride=1: 1
Throw the phosphorus trichloride of 100 grams 98% and go in the pressure reaction still, under the condition of secluding air and water, control 20～110 ℃; Drip the methyl chloride/chloroform saturated solution of calculated amount, insulation reaction boiled off chloroform solvent after 2 hours; Leave standstill, crystallization is filtered; Dry; Get season
Figure BSA00000237064100132
salt 6 solids, yield 98%, content 98%.
Cause 6 is unstable in empty G&W, again it is dissolved in the ethylene dichloride, and controlled temperature is below 20 ℃; Slowly adding waits the aluminum chloride of mol, and insulation reaction dripped Vanadium Pentoxide in FLAKES after 4～8 hours; There are a large amount of throw outs to separate out, filter, mother liquor vacuum distilling; The distillation substrate is 8 compounds, yield 98%, content 98%.
Embodiment 2
Throw the phosphorus trichloride of 100 grams 98% and go in the reaction flask, under the condition of secluding air and water, controlled temperature drips the methyl chloride tripotassium phosphate ester solution of calculated amount 20～40% below 54 ℃; When a step generates 8 compounds, there is hydrogenchloride to produce, react after 4～8 hours, there are a large amount of solids to separate out; Leave standstill, vacuum-drying is filtered in crystallization; Get 8 compounds, yield 98%, content 98%.
Embodiment 3
8 and trimethyl phosphite 99 of embodiment 2 preparations are prepared 10～20% solution, drop in the reaction flask, controlled temperature is below 5 ℃, and the benzophenone of mol such as dropping reacted after 2 hours, generates 1,1-toluylene and POCl3, yield 85%.
Embodiment 4
20 grams, 9 compounds and sodium methylate that waits mol and 100ml THF are dropped in the reaction flask, and below the controlled temperature-10 ℃, stirring reaction dripped acetaldehyde after 20 hours, react after 2 hours and separated, and got 11 compounds, yield 90%, content 90%.
Embodiment 5
The molecule proportioning, phosphorus trichloride: methylamine=1: 1
Drop into the phosphorus trichloride of 50 grams 98% and go in the reaction flask, start and stir, controlled temperature-10～50 ℃; Drip 20～40% methylamine trimethyl phosphite 99 solution of calculated amount, react after 10～20 hours, add 2～5 times of methylals (99%) to the trimethyl phosphite 99 quality; Reaction solution is divided into two layers; Isolate lower floor, obtain 27 compounds, yield 98%.
Embodiment 6
Methyl dichloro phosphine 40 grams of throwing 99% are gone in the reaction flask, and 20～40 gram trimethyl phosphite 99s start and stir, and controlled temperature is below 20 ℃; Drip hydroxy propanal 26 grams, react 1～16 hour, drip 6.5 gram water then, 30～40 ℃ react 2 hours after; Cooling is left standstill, and crystallization is filtered; Drying gets 18 compounds, 43 grams, content 98%.
18 compounds, 20 grams are dropped in the reaction flask, start and stir, slowly adding waits ammonium chloride and the sodium cyanide solution of mol, and 30～60 ℃ of controlled temperature reacted 4～8 hours, generated 19 compounds, yield 90%, and alkaline hydrolysis generates careless ammonium phosphine then, yield 90%.
Embodiment 7
Throwing 40 gram allyl aldehydes and 40 gram normal hexanes are gone in the reaction flask, and start and stir, 20～40 ℃ of controlled temperature, 21 compounds, 68 grams of dropping 98% reacted 4～8 hours, dripped 13 gram water then, and stirring reaction 2 hours generates 18 compounds, yield 92%.
Embodiment 8
Throwing 40 gram allyl aldehydes and 80 gram toluene are gone in the reaction flask, 0～20 ℃, slowly feed PH 3Gas reacted after 2～4 hours, stopped to feed PH 3Gas generates 26 compounds, slowly feeds CH 3Cl gas after the reaction to terminal, generates 29 compounds, and bubbling air constantly generates 18 compounds, yield 90% again.
Embodiment 9
Throw 40 gram allyl aldehydes and 80 gram acetonitriles, and wait the mol sodium methylate to go in the reaction flask, start stirring, 30～60 ℃ of controlled temperature; The HCN acetonitrile solution of mol such as dropping reacted after 2～4 hours, generated 22 compounds, yield 90%; Drip 21 compounds then, continue reaction 4～16 hours, generate 24 compounds, yield 95%; With the abundant hydrolysis under acidic conditions of 24 compounds, crystallization, filtration, drying obtain the former medicine of careless ammonium phosphine, content 98%.
Embodiment 10
22 compounds, 20 grams and normal hexane 60 grams are dropped in the reaction flask, and 0～20 ℃ of controlled temperature slowly feeds PH 3Gas with 22 content≤1% in the liquid chromatography normalization method analytical reaction system o'clock, is terminal point, stops to feed PH 3Gas, the resultant of this moment is 25 compounds, yield 98%; Slowly feed methyl chloride gas again,, stop to feed methyl chloride gas with 25 content≤1% in the liquid chromatography normalization method analytical reaction system o'clock; Slowly aerating oxygen or air again; Generate 19 compounds, add the abundant hydrolysis of buck, obtain careless ammonium phosphine.
Embodiment 11
8 compounds and normal hexane be mixed with 50% solution and drop in the pressure reaction still, nitrogen protection, 0～20 ℃ of controlled temperature slowly adds equimolar thiophosgene, reacts 8～20 hours, generates 30 compounds, yield 80%.

Claims (5)

1. innovate compound 2,8,10,27,16,17,18,21,26,29,22,25,5,30 have following structural:
Figure FSA00000237064000011
X representes halogen atom in 5, phenyl, H; Z representes halogen atom, phenyl, H; Wait other not contain O, all electron-withdrawing groups of S atom; R representes all alkylates.
2. according to claim 1, utilize 2,8,5 compounds to carry out Wittig reaction:
Figure FSA00000237064000021
Among the formula C, X representes halogen atom, phenyl; H; Z representes halogen atom, phenyl, H; Wait other not contain O, all electron-withdrawing groups of S atom; R representes all alkylates,
One of classical reaction comprises the several steps of following order:
Figure FSA00000237064000022
Figure FSA00000237064000023
Figure FSA00000237064000024
Above-mentioned reaction also can A, B, C, D step merge into a step cascade reaction.
3. prepare new Wittig-Horner reagent, comprise the several steps of following order:
A selects
Figure FSA00000237064000031
12 or 13 compounds meet following prerequisite:
R or R 1Or Z can not with highly basic generation chemical reaction, perhaps can be not under preparation process condition and highly basic generation chemical reaction;
Z representes strong electron-withdrawing group group in 12 and 13, and trichlorophenyl, nitrophenyl, halogen atom are arranged-CN; Or the like;
14 and 15 expression Wittig-Horner reagent general formulas, M representes highly basic in the following formula, and NaH is for example arranged, PhLi, NaNH 2, C 2H 5ONa, NaOH-EtOH etc.
4. according to claim 1, utilize 27 compounds to carry out the Aza-wittig reaction:
The LJ reaction:
Figure FSA00000237064000041
27 is a kind of new phosphorus imines ylide reagent, and R representes various alkylates.
5.2.1. careless ammonium phosphine is synthetic, comprises the several steps of following order:
A LJ reaction
Figure FSA00000237064000042
16,17,18 are the innovation compound
Figure FSA00000237064000043
C, the reaction of Shi Te Rec
Figure FSA00000237064000044
R representes in the formula: H,
Figure FSA00000237064000045
D、
Figure FSA00000237064000051
2.2 careless ammonium phosphine is synthetic, comprises the several steps of following order:
A LJ reaction
Figure FSA00000237064000052
21 are the innovation compound,
20+ tetramethyl plumbane or trimethylaluminium-→ 21
Figure FSA00000237064000053
29+H 2O or air---→ 18
B, identical with the 2.1B step
C, identical with the 2.1C step
D, identical with the 2.1D step
2.3 careless ammonium phosphine is synthetic, comprises the several steps of following order
The reaction of A Shi Te Rec
Figure FSA00000237064000061
R representes
Figure FSA00000237064000062
H in the formula
22 are the innovation compound
Figure FSA00000237064000063
C, existing bibliographical information, 23 and 24 all is the midbody of the careless ammonium phosphine of preparation, methylate and hydrolysis after promptly transform into careless ammonium phosphine;
Figure FSA00000237064000064
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CN103539815A (en) * 2013-10-14 2014-01-29 苏州联合伟业科技有限公司 Preparation method of 4-(hydroxy-(methyl)phosphinyl)-2-oxobutyric acid
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CN107417721B (en) * 2016-05-24 2019-05-28 四川福思达生物技术开发有限责任公司 A kind of hydrogen cyanide additive process
CN107602608A (en) * 2017-09-26 2018-01-19 安徽国星生物化学有限公司 A kind of preparation method of diethyl methyl-phosphonite
CN109164192A (en) * 2018-10-26 2019-01-08 四川福思达生物技术开发有限责任公司 A method of measurement dichloromethylphosphine content
CN109164192B (en) * 2018-10-26 2021-10-12 四川福思达生物技术开发有限责任公司 Method for determining content of methyl phosphine dichloride

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